Process for the preparation of monodisperse polymer particles

• US 7,217,762 B1
• Filed: 04/10/2000
• Issued: 05/15/2007
• Est. Priority Date: 04/09/1999
• Status: Expired due to Term

• Current Assignee: Life Technologies AS (Perspecta, Inc.)
• Original Assignee: Invitrogen Corp. (Thermo Fisher Scientific Incorporated)
• Inventors: Hansen, Finn Knut, Berge, Arvid Trygve, Aksnes, Elin Marie, Weng, Ellen, Fonnum, Geir, Aune, Oddvar Arnfinn, Nordal, Rolf, Ugelstad, legal representative, Molteberg, Astrid Evenro, Pettersen, Henning, Berge, legal representative, Taarneby, Tollef, Nordbo, Silje Steinbakk, Ellingsen, deceased, Staale, Solveig Marle, Ugelstad, deceased, Jorgedal, Arne, Bjorgum, John Olav
• Primary Examiner(s): Cain; Edward J.
• Application Number:
  US09/958,431
• Time in Patent Office: 2,591 Days
• Field of Search: 524/800, 524/802, 524/804, 524/812, 524/819, 524/822, 524/823, 524/832
• US Class Current: 524/800
• CPC Class Codes: C08F 2/22 Emulsion polymerisation
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 265/10 on to polymers of amides or imides
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08J 2203/14 Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
• CPC Class Codes: C08J 2325/06 Polystyrene
• CPC Class Codes: C08J 2347/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers C08J2345/00 takes precedence; of conjugated diene rubbers C08J2309/00 - C08J2321/00
• CPC Class Codes: C08J 9/16 Making expandable particles
• CPC Class Codes: C08J 9/22 After-treatment of expandable particles; Forming foamed products
• CPC Class Codes: C08J 9/224 Surface treatment

Abstract

A process for the preparation of monodisperse polymer particles which are formed by contacting monomers with aqueous dispersions comprising monodisperse swellable seed polymers/oligomers, and initiating polymerization in the presence of a steric stabilizer. The resulting swollen seed particles are characterized by the particle mode diameter.

Claims

1. A process for the preparation of monodisperse polymer particles having diameters of 1 to 6 μ

m which process comprises;

forming an aqueous dispersion comprising monodisperse swellable seed particles, an anionic surfactant, and droplets comprising dioctanoyl peroxide;

contacting the aqueous dispersion of seed particles with a monomer selected from the group consisting of acrylic monomers, methacrylate monomers and vinyl monomers selected from the group consisting of styrene, divinylbenzene (DVB), ethyl vinyl benzene, vinyl pyridine, amino-styrene, methyl-styrene, dimethylstyrene, ethyl styrene, ethyl-methyl-styrene, p-chlorostyrene and 2,4-dichlorostyrene;

allowing the monomer to diffuse into the seed particles to form an aqueous dispersion of swollen seed particles; and

initiating polymerization of the monomer in the aqueous dispersion of swollen seed particles wherein the aqueous phase of the aqueous dispersion of swollen seed particles during polymerisation further containing as a steric stabilizer a polyvinylpyrrolidone.

78. The process of claim 1, wherein the dioctanyl peroxide diffuses into the seed particles.

79. The process of claim 1, wherein the aqueous dispersion is contacted with a porogen.

80. The process of claim 1, wheirne the monomer comprises about 30% by weight divinyl benzene.

81. The process of claim 1, wherein the anionic surfactant is sodium dodecyl sulfate.

82. The process of claim 1, further comprising the step of coating the monodisperse polymer particles.

83. The process of claim 1, further comprising the step of impregnating the monodisperse polymer particles.

84. The process of claim 1, further comprising the step of derivatizing the monodisperse polymer particles.

2. A process for the preparation of monodisperse polymer particles having diameters of 1 to 6 μ

m which process comprises;

forming an aqueous dispersion comprising monodisperse swellable seed particles and an anionic surfactant;

contacting the aqueous dispersion of seed particles with a monomer selected from the group consisting of acrylic monomers, methacrylate monomers and vinyl monomers selected from the group consisting of styrene, divinylbenzene (DVB), ethyl vinyl benzene, vinyl pyridine, amino-styrene, methyl-styrene, dimethylstyrene, ethyl styrene, ethyl-methyl-styrene, p-chlorostyrene and 2,4-dichlorostyrene;

allowing the monomer to diffuse into the seed particles to form an aqueous dispersion of swollen seed particles; and

initiating polymerization of the monomer in the aqueous dispersion of swollen seed particles wherein the aqueous phase of the aqueous dispersion of swollen seed particles during polymerisation further contains as a steric stabilizer a polyvinylpyrrolidone;

wherein the monodisperse swellable seed particles are monodisperse swellable seed oligomer particles.

85. The process of claim 2, wherein the aqueous dispersion is contacted with a porogen.

86. The process of claim 2, wherein the monomer comprises about 30% by weight divinyl benzene.

87. The process of claim 2, wherein the anionic surfactant is sodium dodecyl sulfate.

88. The process of claim 2, further comprising the step of coating the monodisperse polymer particles.

89. The process of claim 2, further comprising the step of impregnating the monodisperse polymer particles.

90. The process of claim 2, further comprising the step of derivatizing the monodisperse polymer particles.

3. A process for the preparation of monodisperse polymer particles having diameters of 1 to 6 μ

m which process comprises;

forming an aqueous dispersion comprising monodisperse swellable seed particles, an anionic surfactant, and droplets comprising dioctyladipate;

contacting the aqueous dispersion of seed particles with a monomer selected from the group consisting of acrylic monomers, methacrylate monomers and vinyl monomers selected from the group consisting of styrene, divinylbenzene (DVB), ethyl vinyl benzene, vinyl pyridine, amino-styrene, methyl-styrene, dimethylstyrene, ethyl styrene, ethyl-methyl-styrene, p-chlorostyrene and 2,4-dichlorostyrene;

allowing the monomer to diffuse into the seed particles to form an aqueous dispersion of swollen seed particles; and

initiating polymerization of the monomer in the aqueous dispersion of swollen seed particles wherein the aqueous phase of the aqueous dispersion of swollen seed particles during polymerisation further contains as a steric stabilizer a polyvinylpyrrolidone;

wherein the monomer is an amino-functionalized monomer and a polymerization initiator is added after the seed particles have been swollen.

91. The process of claim 3, wherein the dioctanyl peroxide diffuses into the seed particles.

92. The process of claim 3, wherein the aqueous dispersion is contacted with a porogen.

93. The process of claim 3, wherein the monomer comprises about 30% by weight divinyl benzene.

94. The process of claim 3, wherein the anionic surfactant is sodium dodecyl sulfate.

95. The process of claim 3, further comprising the step of coating the monodisperse polymer particles.

96. The process of claim 3, further comprising the step of impregnating the monodisperse polymer particles.

97. The process of claim 3, further comprising the step of derivatizing the monodisperse polymer particles.

98. The process of claim 3, wherein the polymerization initiator is 2,2′

-azobis-(2-methylbutyronitrile).

4. A process for the preparation of monodisperse polymer particles which process comprises:

forming an aqueous dispersion comprising monodisperse swellable seed particles and an anionic surfactant;

contacting the aqueous dispersion of seed particles with a monomer;

allowing the monomer to diffuse into the seed particles to form an aqueous dispersion of swollen seed particles having a mode diameter in the range 5 to 200 μ

m; and

initiating polymerization of the monomer in the aqueous dispersion of swollen seed particles, wherein the aqueous phase of the aqueous dispersion of swollen seed particles during polymerisation further contains as a steric stabilizer a water soluble cellulose ether of weight average molecular weight 10 to 100 kD.

5. The process of claim 4 wherein the water soluble cellulose ether is a hydroxy propylmethyl cellulose.

6. The process of claim 4 wherein the mode diameter of the swollen seed particles is in a range of 15 to 200 μ

m.

7. The process of claim 4 wherein the aqueous dispersion comprises droplets comprising an organic compound with a molecular weight below 5000 Dalton and a water solubility at 25°

C. of less than 10<sup>−

2</sup> g/L.

8. The process of claim 7 wherein said aqueous dispersion comprises an organic solvent.

9. The process of claim 7, further comprising the step of allowing the organic compound to diffuse into the seed particles.

10. The process of claim 7, wherein the organic compound is dioctanoyl peroxide.

11. The process of claim 7, wherein the monomer is at least 10 times more water soluble than the organic compound.

12. The process of claim 4, wherein the aqueous dispersion is contacted with a porogen.

13. The process of claim 4, wherein the aqueous dispersion is contacted with a polymerization initiator.

14. The process of claim 4, wherein the monodisperse swellable seed particles are monodisperse swellable seed oligomer particles.

15. The process of claim 4, wherein the monomer comprises at least 30% by weight divinyl benzene.

16. The process of claim 7, wherein the monomer is an amino-functionalized monomer, the organic compound is an non-initiator, and a polymerization initiator is added after the seed particles have been swollen.

17. The process of claim 16 wherein the non-initiator is dioctyladipate.

18. The process of claim 16 wherein the polymerization initiator is 2,2′

-azobis-(2-methylbutyronitrile).

19. The process of claim 4 wherein the anionic surfactant is sodium dodecyl sulphate.

20. The process of claim 4, further comprising the step of coating the monodisperse polymer particles.

21. The process of claim 4, further comprising the step of impregnating the monodisperse polymer particles.

22. The process of claim 4, further comprising the step of derivatizing the monodisperse polymer particles.

55. The process of claim 16, further comprising the step of coating the monodisperse polymer particles.

56. The process of claim 16, further comprising the step of impregnating the monodisperse polymer particles.

57. The process of claim 16, further comprising the step of derivatizing the monodisperse polymer particles.

23. A process for the preparation of monodisperse polymer particles having a diameter of at least 16 μ

m which process comprises;

forming an aqueous dispersion comprising monodisperse swellable seed particles and an anionic surfactant;

contacting the aqueous dispersion of seed particles with a monomer;

allowing the monomer to diffuse into the seed particles to form an aqueous dispersion of swollen seed particles; and

initiating polymerization of the monomer in the aqueous dispersion of swollen seed particles to produce a polymer, wherein the swollen seed particles contain at least two porogens, at least one of which is a solvent for the polymer produced and at least one of which is not a solvent for the polymer produced and at least one porogen is an aliphatic hydrocarbon having up to 12 carbon atoms.

24. A process as claimed in claim 23 wherein the porogens comprise toluene and n-heptane.

25. The process of claim 23, wherein the aqueous phase of the aqueous dispersion of swollen seed particles during polymerization comprises a steric stabilizer selected from the group consisting of water soluble cellulose ether and polyvinylpyrrolidone.

26. The process of claim 23, wherein the aqueous dispersion comprises droplets comprising an organic compound with a molecular weight below 5000 Dalton and a water solubility at 25°

C. of less than 10<sup>−

5</sup> g/L.

27. The process of claim 26, wherein the aqueous dispersion comprises an organic solvent.

28. The process of claim 26, further comprising the step of allowing the organic compound to diffuse into the seed particles.

29. The process of claim 26, wherein the organic compound is dioctanoyl peroxide.

30. The process of claim 26, wherein the monomer is at least 10 times more water soluble than the organic compound.

31. The process of claim 23, wherein the aqueous dispersion is contacted with a polymerization initiator.

32. The process of claim 23, wherein the monodisperse swellable seed particles are monodisperse swellable seed oligomer particles.

33. The process of claim 23, wherein the monomer comprises at least 30% by weight divinyl benzene.

34. The process of claim 26, wherein the monomer is at amino-functionalized monomer, the organic compound is an non-initiator, and a polymerization initiator is added after the seed particles have been swollen.

35. The process of claim 34, wherein the non-initiator is dioctylapidate.

36. The process of claim 34, wherein the polymerization initiator is 2,2′

-azobis-(2-methylbutyronitrile).

37. The process of claim 23, wherein the anionic surfactant is sodium dodecyl sulfate.

38. The processor of claim 23, further comprising the step of coating the monodisperse polymer particles.

39. The process of claim 23, further comprising the step of impregnating the monodisperse polymer particles.

40. The process of claim 23, further comprising the step of derivatizing the monodisperse polymer particles.

58. The process of claim 34, further comprising the step of coating the monodisperse polymer particles.

59. The process of claim 34, further comprising the step of impregnating the monodisperse polymer particles.

60. The process of claim 34, further comprising the step of derivatizing the monodisperse polymer particles.

41. A process for the preparation of monodisperse polymer particles which process comprises

forming an aqueous dispersion comprising monodisperse swellable seed particles and an anionic surfactant;

contacting the aqueous dispersion of seed particles with at least two monomers;

allowing the monomers to diffuse into the seed particles to form an aqueous dispersion of swollen seed particles that swell at least 3.5 times in diameter; and

imitating polymerization of the monomers in the aqueous dispersion of swollen seed particles to produce polymer particles;

wherein at least two monomers are selected from the group consisting of acrylic, methacrylic acid and ester monomers and combinations of these monomers; and

wherein the aqueous phase of the aqueous dispersion of swollen seed particles during polymerisation further contains a steric stabilizer.

42. The process of claim 41, wherein at least one of the monomers is glycidyl methacrylate.

43. The process of claim 41, wherein the aqueous dispersion comprises droplets comprising an organic compound with a molecular weight below 5000 Dalton and a water solubility at 25°

C. of less than 10<sup>−

2</sup> g/L and optionally an organic solvent.

44. The process of claim 43, wherein the monomer is at least 10 times more water soluble than the organic compound.

45. The process of claim 43, wherein at least one of the monomers is an amino-functionalized monomer, the organic compound is an non-initiator, and a polymerization initiator is added after the seed particles has been swollen.

46. The process of claim 45, wherein the non-initiator is dioctylapidate.

47. The process of claim 45, wherein the polymerization initiator is 2,2′

-azobis-(2-methylbutyronitrile).

48. The process of claim 41, wherein the anionic surfactant is sodium dodecyl sulfate.

49. The process of claim 41, further comprising the step of coating the monodisperse polymer particles.

50. The process of claim 41, further comprising the step of impregnating the monodisperse polymer particles.

51. The process of claim 41, further comprising the step of derivatizing the monodisperse polymer particles.

52. The process of claim 41, wherein the aqueous dispersion is contacted with a porogen.

53. The process of claim 41, wherein the monodisperse swellable seed particles are monodisperse swellable seed oligomer particles.

64. The process of claim 41, wherein the steric stabilizer is selected from the group consisting of water soluble cellulose ether and polyvinylpyrrolidone.

54. A method of cleaning monodisperse polymer particles produced by swelling seed particles in an aqueous dispersion and polymerizing a monomer with swollen seed particles, the method comprising contacting the monodisperse polymer particles with butyl acetate.

61. A process for the preparation of monodisperse seed particles, the process comprising:

emulsion polymerising monomer in an aqueous dispersion in the presence of an anionic surfactant employed as an emulsifier under substantially oxygen free conditions to form swellable seed particles having a mode diameter in the range 0.2 to 1μ

m.

62. The process of claim 61 wherein the anionic surfactant is sodium decyl sulphate.

63. The process of claim 61, wherein an aqueous phase of the aqueous dispersion has an oxygen content of between 0 and 5 ppm.

65. The process of claim 61, wherein an aqueous phase of the aqueous dispersion has an oxygen content of between 0 and 1 ppm.

66. The process of claim 61, further comprising the steps of:

contacting the seed particles with an aqueous dispersion comprising an organic compound with a molecular weight below 5000 Dalton and a water solubility at 25°

C. of less than 10<sup>−

2</sup> g/L and an anionic surfactant; and

allowing the organic compound to diffuse into the seed particles;

contacting the aqueous dispersion of seed particles with a monomer which is at dispersion of swollen seed particles; and

initiating polymerization of the monomer in the aqueous dispersion of swollen seed particles containing a steric stabiliser in the continuous phase to produce a polymer.

67. The process of claim 66, wherein the aqueous dispersion comprises an organic solvent.

68. The process of claim 66, wherein the aqueous dispersion is contacted with a porogen.

69. The process of claim 66, wherein the aqueous dispersion is contacted with a polymerization initiator.

70. The process of claim 66, wherein the monomer is an amino-functionalized monomer, the organic compound is an non-initiator, and a polymerization initiator is added after the seed particles have been swollen.

71. The process of claim 70, wherein the non-initiator is dioctylapidate.

72. The process of claim 70, wherein the polymerization initiator is 2,2′

-azobis-(2-methylbutyronitrile).

73. The process of claim 66, wherein the anionic surfactant is sodium dodecyl sulfate.

74. The process of claim 66, further comprising the step of coating the monodisperse polymer particles.

75. The process of claim 66, further comprising the step of impregnating the monodisperse polymer particles.

76. The process of claim 66, further comprising the step of derivatizing the monodisperse polymer particles.

77. The process of claim 66, wherein the organic compound is dioctanoyl peroxide.