Opacifying particles with internal void and methods for making the same
View Patent ↗The invention includes a method of preparing an aqueous dispersion of particles at least partially encapsulated by a polymer, the method comprising dispersing inorganic particles in an aqueous phase; functionalizing at least a portion of the surfaces of the inorganic particles with a coupling agent, the coupling agent having pendent reactive groups; polymerizing the reactive groups on the functionalized particles with a first polymerizable component to produce inner polymer shells surrounding the inorganic particles; polymerizing a second polymerizable component to form outer polymer shells at least partially encapsulating the inner polymer shells; and producing voids within the outer polymer shells, such that the inorganic particles are received within the voids.
1. An aqueous dispersion of particles comprising:
inorganic particles, each particle being at least partially encapsulated by an inner shell, wherein at least a portion of the surface of each particle comprises a coupling agent having a pendent reactive group, and wherein the inner shell is prepared from a reaction of the coupling agent pendent reactive group with an ethylenically unsaturated monomer;
a first outer shell at least partially encapsulating each inner shell, the first outer shell defining a void; and
a plurality of second outer polymer shells at least partially encapsulating the first outer shell, wherein the second outer polymer shells are at least partially spaced apart from the first outer shell by the void.
2. The aqueous dispersion of claim 1 , wherein the coupling agent comprises a silane coupling agent.
3. The aqueous dispersion of claim 2 , wherein the coupling agent pendent reactive group comprises ethylenic unsaturation.
4. The aqueous dispersion of claim 3 , wherein the coupling agent comprising ethylenic unsaturation comprises monomers of a C 1 -C 12 alkyl ester of (meth)acrylic acid.
5. The aqueous dispersion of claim 2 , wherein the silane coupling agent comprises a hydrolysable group which, upon hydrolysis, comprises a residue with free hydroxyl groups present on the inorganic particle surfaces.
6. The aqueous dispersion of claim 2 , wherein the outer polymer shells each comprise polystyrene.
7. The aqueous dispersion of claim 2 , wherein the inorganic particles comprise titanium dioxide.
8. A coating composition comprising the aqueous dispersion of claim 2 .
9. A method of preparing an aqueous dispersion of particles at least partially encapsulated by a polymer, according to claim 1 the method comprising:
dispersing inorganic particles in an aqueous phase;
functionalizing at least a portion of the surfaces of the inorganic particles with a monomeric coupling agent, the coupling agent having a pendent reactive group;
polymerizing the reactive groups on the functionalized particles with a first polymerizable component to produce an inner polymer shell at least partially encapsulating each inorganic particle, wherein the inner polymer shell is prepared from a reaction of the coupling agent pendent reactive group with an ethylenically unsaturated monomer;
polymerizing a second polymerizable component to form a first outer polymer shell at least partially encapsulating each inner polymer shell;
polymerizing additional polymerizable components to form a plurality of second outer polymer shells at least partially encapsulating each first outer polymer shell; and
producing voids within the first outer polymer shell, wherein the second outer polymer shells are at least partially spaced apart from the first outer polymer shell by the voids.
10. The method of claim 9 , wherein said step of producing voids comprises (i) expanding the first outer polymer shells and the second outer polymer shells and (ii) shrinking the expanded first outer polymer shells thereby forming the voids within the first outer polymer shells.
11. The method of claim 10 , further comprising crosslinking the expanded second outer shells.
12. The method of claim 11 , wherein the additional polymerizable component comprises styrene, methyl methacrylate, and/or acrylonitrile.
13. The method of claim 12 , wherein the expanded second outer polymer shells comprise an expanded second outer shell comprising polystyrene and another expanded outer second shell comprising cross-linked polystyrene, wherein the other second expanded outer shells at least partially encapsulate the first expanded outer shells.
14. The method of claim 9 , wherein the coupling agent comprises a silane coupling agent.
15. The method of claim 14 , wherein the coupling agent pendent reactive group comprises ethylenic unsaturation.
16. The method of claim 15 , wherein the first polymerizable component comprises ethylenically unsaturated monomers.
17. The method of claim 16 , wherein the coupling agent comprising ethylenically unsaturated monomers comprises monomers of a C 1 -C 12 alkyl ester of (meth)acrylic acid.
18. The method of claim 14 , wherein the silane coupling agent comprises a hydrolysable group which, upon hydrolysis, comprises a residue reactive with free hydroxyl groups present on the inorganic particle surfaces.