Polymerisable mass with cross-linking nanoparticles
View Patent ↗The invention provides a polymerizable composition which comprises: a) acrylates and/or methacrylates, b) 0.05% to 70% by weight of SiO 2 particles having an average particle size of 1 to 30 nm which have polymerizable groups of the methacryloyl, acryloyl, styryl, itaconyl, crotonyl, vinyl, allyl and/or alkenyl type on the surface and are present in dispersion in the acrylates and/or methacrylates, at least 50% of the SiO 2 particles consisting of individual, unaggregated or unagglomerated primary particles, c) not more than 2% by weight of crosslinker molecules.
1. A polymerizable composition comprising:
a) acrylates and/or methacrylates,
b) 0.05% to 70% by weight of SiO 2 particles having an average particle size of 1 to 30 nm which have polymerizable groups of the methacryloyl, acryloyl, styryl, itaconyl, crotonyl, vinyl, allyl and/or alkenyl type on the surface and are present in dispersion in the acrylates and/or methacrylates, at least 50% of the SiO 2 particles consisting of individual, unaggregated or unagglomerated primary particles,
c) not more than 2% by weight of crosslinker molecules.
2. The polymerizable composition of claim 1 , wherein the polymerizable composition comprises 50% to 99.5% by weight of the acrylates and/or methacrylates.
3. The polymerizable composition of claim 2 , wherein the polymerizable composition comprises at least 60% by weight of methyl methacrylate.
4. The polymerizable composition of claim 2 , wherein the polymerizable composition comprises at least 70% by weight of methyl methacrylate.
5. The polymerizable composition of claim 2 , wherein the polymerizable composition comprises at least 80% by weight of methyl methacrylate.
6. The polymerizable composition of claim 1 , wherein the average particle size of the SiO 2 particles is at least 2 nm.
7. The polymerizable composition of claim 1 , wherein the average particle size of the SiO 2 particles is at least 3 nm.
8. The polymerizable composition of claim 1 , wherein the average particle size of the SiO 2 particles is at least 4 nm.
9. The polymerizable composition of claim 1 , wherein the average particle size of the SiO 2 particles is at least 5 nm.
10. The polymerizable composition of claim 1 , wherein the average particle size of the SiO 2 particles is 25 nm.
11. The polymerizable composition of claim 1 , wherein the average particle size of the SiO 2 particles is not more than 20 nm.
12. The polymerizable composition of claim 1 , wherein the SiO 2 particles have polymerizable groups in a concentration of 0.01-10 groups/nm 2 on the surface of the particles.
13. The polymerizable composition of claim 1 , wherein the SiO 2 particles have polymerizable groups in a concentration of 0.01-6 groups/nm 2 on the surface of the particles.
14. The polymerizable composition of claim 1 , wherein the SiO 2 particles have polymerizable groups in a concentration of 0.01-4 groups/nm 2 on the surface of the particles.
15. The polymerizable composition of claim 1 , wherein at least 70% of the SiO 2 particles consist of individual, unaggregated or unagglomerated primary particles.
16. The polymerizable composition of claim 1 , wherein at least 80% of the SiO 2 particles consist of individual, unaggregated or unagglomerated primary particles.
17. The polymerizable composition of claim 1 , wherein at least 90% of the SiO 2 particles consist of individual, unaggregated or unagglomerated primary particles.
18. The polymerizable composition of claim 1 , wherein at least two different polymerizable groups are disposed on the surface of the SiO 2 particles.
19. The polymerizable composition of claim 18 , wherein the at least two different polymerizable groups comprise a first polymerizable group selected from acryloyl, methacryloyl, itaconyl and/or styryl groups, and a second polymerizable group selected from crotonyl, vinyl, allyl and/or alkenyl groups.
20. The polymerizable composition of claim 19 , wherein a fraction of the acryloyl, methacryloyl, itaconyl and/or styryl groups as a proportion of the polymerizable groups on the surface is 95% to 5% and a fraction of the crotonyl, vinyl, allyl and/or alkenyl groups as a proportion of the polymerizable groups on the surface is 5% to 95%.
21. The polymerizable composition of claim 18 , wherein the SiO 2 particles have 0.01-3 methacryloyl groups and 0.01-3 vinyl groups/nm 2 on the surface.
22. The polymerizable composition of claim 1 , further comprising the depolymerization retardant monomers selected from the group consisting of C1 to C8 alkyl acrylates, styrene, itatonates, N-alkylmaleimides, and N-arylmaleimides.
23. The polymerizable composition of claim 1 , further comprising the depolymerization retardant monomers selected from the group consisting of methyl, ethyl, butyl, and 2-ethylhexyl acrylate.
24. The polymerizable composition of claim 22 , wherein the polymerizable composition comprises 0.1% to 20% by weight of the depolymerization retardant monomers.
25. The polymerizable composition of claim 22 , wherein the polymerizable composition comprises 0.2% to 10% by weight of the depolymerization retardant monomers.
26. The polymerizable composition of claim 22 , wherein the polymerizable composition comprises 0.5% to 5% by weight of the depolymerization retardant monomers.
27. The polymerizable composition of claim 1 , wherein a fraction of the crosslinker molecules is not more than 1% by weight.
28. The polymerizable composition of claim 1 , wherein a fraction of the crosslinker molecules is not more than 0.5% by weight.
29. The polymerizable composition of claim 1 , wherein a fraction of the crosslinker molecules is not more than 0.2% by weight.
30. The polymerizable composition of claim 1 , wherein an amount of SiO 2 particles is 0.05% to 5% by weight.
31. The polymerizable composition of claim 1 , wherein an amount of SiO 2 particles is 0.05% to 3% by weight.
32. The polymerizable composition of claim 1 , wherein an amount of SiO 2 particles is 0.1% to 2% by weight.
33. A composition comprising a polymeric material obtainable by curing the polymerizable composition of claim 1 .
34. The composition of claim 33 , wherein the polymeric material is a thermoformable article, a shape memory material, or a stretched glazing material.
35. The composition of claim 33 , prepared by a process comprising the steps of:
a) heating the polymeric material to a temperature T>T g ;
b) elongating or compressing the polymeric material by at least 5% in at least one spatial direction;
c) cooling the polymeric material under load to a temperature T<T g .
36. The composition of claim 35 , wherein the process comprises heating the polymeric material to a temperature T>T g +10 K.
37. The composition of claim 35 , wherein the process comprises heating the polymeric material to a temperature T>T g +40 K.
38. The composition of claim 35 , wherein the process comprises heating the polymeric material to a temperature T>T g +50 K.
39. The composition of claim 35 , wherein the process comprises elongating or compressing the polymeric material by at least 10% in at least one spatial direction.
40. A method of producing glazing or a medical material, comprising the steps of:
a) providing a polymerizable composition according to claim 1 ; and
b) curing the polymerizable composition to produce glazing or a medical material.
41. A process for producing the composition of claim 33 comprising the steps of:
a) providing the polymerizable composition of claim 1 ;
b) adding a polymerization initiator;
c) implementing a partial polymerization at a temperature T<T g until at least 50% of the monomers used are polymerized;
d) completing the polymerization at a temperature T>T g −20 K.
42. The process of claim 41 , wherein the process comprises implementing a partial polymerization at a temperature T<T g −10 K.
43. The process of claim 41 , wherein the process comprises implementing a partial polymerization at a temperature T<T g −20K.
44. The process of claim 41 , wherein the process comprises completing the polymerization at a temperature T>T g −10 K.
45. The process of claim 41 , wherein the process comprises completing the polymerization at a temperature T>T g .
46. The process of claim 41 , further comprising the following steps:
e) heating the polymeric material to a temperature T>T g ;
f) elongating or compressing the polymeric material by at least 5% in at least one spatial direction;
g) cooling the polymeric material under load to a temperature T<T g .
47. The process of claim 46 , wherein the process comprises heating the polymeric material to a temperature T>T g +10 K.
48. The process of claim 46 , wherein the process comprises heating the polymeric material to a temperature T>T g +40 K.
49. The process of claim 46 , wherein the process comprises heating the polymeric material to a temperature T>T g +50 K.
50. The process of claim 46 , wherein the process comprises elongating or compressing the polymeric material by at least 10% in at least one spatial direction.