Functionalized nanoparticles
View Patent ↗The present invention discloses functionalized nanoparticles comprising on the surface a covalently bound radical of the formula (I) wherein the nanoparticles are SiO 2 , Al 2 O 3 or mixed SiO 2 and Al 2 O 3 nanoparticles, and wherein the general symbols are as defined in claim 1 . These functionalized nanoparticles are for example useful as stabilizers and/or compatibilizers in organic materials, or as photoinitiators in pre-polymeric or pre-crosslinking formulations, or as reinforcer of coatings and improver of scratch resistance in coating compositions for surfaces.
1. A functionalized nanoparticle comprising on a surface covalently bound radical of the formula (I) and a covalently bound radical of formula (II):
wherein the functionalized nanoparticle is a SiO 2 nanoparticle;
X is oxygen; sulfur; or
R 1 is a photoinitiator having as formula selected from the group consisting of
R 2 and R 3 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; —OR 5 ;
R 4 is hydrogen; C 1 -C 25 alkyl; or C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur;
R 5 is hydrogen; C 1 -C 25 alkyl; which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 phenylalkyl;
or the nanoparticle surface,
R 6 and R 7 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 phenyl; C 7 -C 9 -phenylalkyl; or —OR 5 ;
R 8 , R 9 and R 10 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; or C 7 -C 9 phenylalkyl;
R 11 is C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen, sulfur or
amino-, mercapto-, or hydroxyl substituted C 2 -C 24 alkyl; amino-, mercapto-, or hydroxyl substituted C 2 -C 24 alkyl, which is interrupted by oxygen, sulfur, or
C 2 -C 24 alkenyl; C 5 -C 12 cycloalkyl; C 5 -C 2 cycloalkenyl; a polymerizable group; or a polymer;
R 12 and R 13 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; —OR 15 ;
R 14 is hydrogen; C 1 -C 25 alkyl; or C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur;
R 15 is hydrogen; C 1 -C 25 alkyl; C 3 -C 75 alkyl, which is interrupted by oxygen or sulfur;
C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl;
or the nanoparticle surface,
R 16 and R 17 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; —OR 15 ,
R 18 , R 19 and R 20 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; or C 7 -C 9 phenylalkyl,
R 43 and R 44 are each independently hydrogen; C 1 -C 18 alkoxy; or di(C 1 -C 4 alkyl)amino;
R 45 is hydrogen; C 1 -C 18 alkyl; or C 1 -C 18 alkoxy;
R 63 and R 64 are each independently hydrogen; C 1 -C 18 alkoxy; C 1 -C 4 alkylthio; morpholinyl; or C 7 -C 9 phenylalkyl of phenyl;
R 65 and R 66 are each independently C 1 -C 18 alkyl;
R 67 is C 2 -C 4 alkylene;
R 68 is hydrogen or C 1 -C 18 alkyl;
R 69 is C 3 -C 7 alkylene;
R 70 and R 71 are each independently C 1 -C 8 alkyl or C 7 -C 9 -phenylalkyl;
R 72 and R 73 are each independently C 1 -C 8 alkyl; or R 72 and R 73 are together —CH 2 CH 2 —O—CH 2 CH 2 — thus forming with the nitrogen atom to which they are attached a morpholinyl ring;
R 74 is hydrogen; C 1 -C 18 alkyl; or C 7 -C 9 -phenylalkyl; and
n is 1, 2, 3, 4, 5, 6, 7 or 8.
2. The functionalized nanoparticle according to claim 1 , wherein n is 3.
3. The functionalized nanoparticle according to claim 1 , wherein R 4 is hydrogen or C 1 -C 4 alkyl.
4. The functionalized nanoparticle according to claim 1 , wherein
R 11 is C 1 -C 18 alkyl; C 3 -C 18 alkyl, which is interrupted by oxygen or sulfur; or 3-aminopropyl.
5. The functionalized nanoparticle according to claim 1 , wherein the functionalized nanoparticle has a spherical shape.
6. The functionalized nanoparticle according to claim 1 , wherein the functionalized nanoparticle has a particle size of 10 to 1000 nm.
7. A composition comprising:
a component (a), which is an organic material subject to oxidative, thermal, or light induced degradation, and
a component (b), which is at least one functionalized nanoparticle according to claim 1 ,
wherein the composition is a coating composition and
the component (a) is an organic film-forming binder.
8. The composition according to claim 7 , wherein the component (a) is a synthetic polymer.
9. The composition according to claim 7 , wherein the component (b) is present in an amount from 0.01 to 80%, based on a weight of the component (a).
10. The composition according to claim 7 , wherein additional additives are present besides the components (a) and (b).
11. A process for photoinitiating in-situ polymerization or hardening of a pre-polymeric nanocomposite or sol to a nanocomposite material, which comprises incorporating therein, or applying thereto, at least one functionalized nanoparticle according to claim 1 .
12. A functionalized nanoparticle comprising on a surface covalently bound radical of the formula (I) and a covalently bound radical of formula (II):
wherein the functionalized nanoparticle is a SiO 2 nanoparticle;
X is oxygen; sulfur; or
R 1 is a photoinitiator having as formula selected from the group consisting of
R 2 and R 3 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; —OR 5 ;
R 4 is hydrogen; C 1 -C 25 alkyl; or C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur;
R 5 is hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur;
C 2 -C 24 alkenyl; phenyl; C 7 -C 9 phenylalkyl;
or the nanoparticle surface,
R 6 and R 7 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; or —OR 5 ;
R 8 , R 9 and R 10 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; or C 7 -C 9 phenylalkyl;
R 11 is C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen, sulfur or
amino-, mercapto-, or hydroxyl substituted C 2 -C 24 alkyl; amino-, mercapto-, or hydroxyl substituted C 2 -C 24 alkyl, which is interrupted by oxygen, sulfur, or
C 2 -C 24 alkenyl; C 5 -C 12 cycloalkyl; C 5 -C 12 cycloalkenyl; a polymerizable group; or a polymer;
R 12 and R 13 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; —OR 15 ;
R 14 is hydrogen; C 1 -C 25 alkyl; or C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur;
R 15 is hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur;
C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl;
or the nanoparticle surface,
R 16 and R 17 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 15 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; C 7 -C 9 -phenylalkyl; or —OR 15 ,
R 18 , R 19 and R 20 are each independently hydrogen; C 1 -C 25 alkyl; C 3 -C 25 alkyl, which is interrupted by oxygen or sulfur; C 2 -C 24 alkenyl; phenyl; or C 7 -C 9 phenylalkyl,
R 24 is
n is 1, 2, 3, 4, 5, 6, 7 or 8.