Silicon dioxide dispersion
View Patent ↗The invention relates to a silicon dioxide dispersion that comprises a) an outer flowable phase containing 1) polymerizable monomers, oligomers and/or prepolymers that can be converted to polymers by non-radical reaction; and/or 2) polymers, and b) a disperse phase containing amorphous silicon dioxide. The inventive dispersion is characterized in that the average particle size d max of the silicon dioxide as measured by small angle neutron scattering (SANS) is between 3 and 50 nm at a maximum half-width of the distribution curve of 1.5 d max . Such a silicon dioxide dispersion can be easily manufactured even at higher concentrations of the disperse phase and can be used to produce polymer materials that have advantageous properties, especially advantageous mechanical properties.
1. A silicon dioxide dispersion, comprising:
a) an external fluid phase comprising:
i) at least one of polymers and/or polymerizable constituents convertible to polymers by nonradical reactions, said polymerizable constituents selected from a group consisting of polymerizable monomers, oligomers and/or prepolymers, wherein said polymerizable constituents comprise polymerizable monomers that lack radically polymerizable double bonds and/or reactive resins; and
ii) silanes;
and
b) a disperse phase comprising amorphous silicon dioxide particles comprising silanol groups on their surfaces, wherein said disperse phase is from 30-80% by weight of said dispersion;
wherein said silanes in said external phase are present in an amount of 60-150 mol % of the molar amount of the silanol groups on the surface of the amorphous silicon dioxide particles of said disperse phase;
wherein the average particle size d max of said amorphous silicon dioxide particles as measured by small-angle neutron scattering (SANS) is between 3 and 50 nm and wherein the maximum half-width of the distribution curve is not more than 1.5 d max ; and
wherein said dispersion is water-free.
2. The dispersion of claim 1 , wherein the average particle size of said amorphous silicon dioxide particles is between 6 and 40 nm.
3. The dispersion of claim 1 , wherein the average particle size of said amorphous silicon dioxide particles is between 8 and 30 nm.
4. The dispersion of claim 1 , wherein the average particle size of said amorphous silicon dioxide particles is between 10 and 25 nm.
5. The dispersion of claim 1 , wherein the half-width of the distribution curve is not more than 1.2 d max .
6. The dispersion of claim 1 , wherein the half-width of the distribution curve is not more than d max .
7. The dispersion of claim 1 , wherein the half-width of the distribution curve is not more than 0.75 d max .
8. The dispersion of claim 1 , wherein said external fluid phase is from 30 to 70% by weight of said dispersion.
9. The dispersion of claim 1 , wherein said external fluid phase is from 40 to 70% by weight of said dispersion.
10. The dispersion of claim 1 wherein said disperse phase is from 30-70% by weight of said dispersion.
11. The dispersion of claim 1 , wherein said disperse phase is from 30-60% by weight of said dispersion.
12. The dispersion of claim 1 , wherein said amorphous silicon dioxide particles are substantially spherical.
13. The dispersion of claim 1 , further comprising auxiliaries selected from the group consisting of solvents, plasticizers, crosslinkers, catalysts, stabilizers, dispersants, curing agents, reaction mediators, and agents for influencing the fluidity of the dispersion.
14. The dispersion of claim 1 , wherein said external fluid phase comprises at least one substance selected from the group consisting of polyols, polyamines, linear or branched polyglycol ethers, polyesters, and polylactones.
15. The dispersion of claim 1 , wherein said external fluid phase comprises at least one reactive resin.
16. The dispersion of claim 1 , wherein one or more of said polymerizable monomers, oligomers, or prepolymers comprise main chains, and wherein said main chains comprise one or more C, O, N or S atoms.
17. A process for producing a polymeric material comprising the use of a silicon dioxide dispersion of claim 1 .
18. The process of claim 17 , wherein said polymeric material produced is selected from the group consisting of polyurethanes, polyureas, epoxy resins, polyester resins, and polysiloxanes.
19. The process of claim 17 , wherein said polymeric material produced is a thermoset.
20. The process of claim 17 , wherein said polymeric material produced is a thermoplastic.
21. The process of claim 17 , wherein said polymeric material produced comprises a polymeric coating, a paint, an ink, or a foam.
22. A process for preparing a silicon dioxide dispersion, comprising:
a) providing:
i) an aqueous silicate solution,
ii) one or more constituents of an external fluid phase,
b) polycondensing said aqueous silicate solution to a silicate particle size of 3-50 nm to produce a silica sol,
c) adjusting said silica sol to an alkaline pH,
d) mixing said silica sol with said one or more constituents of an external fluid phase to produce a dispersion and
e) removing water from said dispersion to produce a silicon dioxide dispersion comprising:
1) an external fluid phase comprising:
i) at least one of polymers and/or polymerizable constituents convertible to polymers by nonradical reactions, said polymerizable constituents selected from a group consisting of polymerizable monomers, oligomers and/or prepolymers, wherein said polymerizable constituents comprise polymerizable monomers that lack radically polymerizable double bonds and/or reactive resins; and
ii) silanes;
and
2) a disperse phase comprising amorphous silicon dioxide particles comprising silanol groups on their surfaces, wherein said disperse phase is from 30-80% by weight of said dispersion;
wherein said silanes in said external phase are present in an amount of 60-150 mol % of the molar amount of silanol groups on the surface of the amorphous silicon dioxide particles of said disperse phase; and
wherein the average particle size d max of said amorphous silicon dioxide particles as measured by small-angle neutron scattering (SANS) is between 3 and 50 nm and wherein the maximum half-width of the distribution curve is not more than 1.5 d max
wherein said dispersion is water-free.
23. The process of claim 22 , further comprising concentrating said silica sol prior to said mixing of the silica sol with said external fluid phase.
24. The process of claim 22 , further comprising removing other solvent constituents from said dispersion.
25. The process of claim 24 , wherein said silica sol is concentrated to a concentration of 30-40% by weight.
26. The process of claim 22 , wherein said aqueous silicate solution is an alkali metal silicate solution.
27. The process of claim 26 , wherein said alkali metal silicate solution comprises a sodium silicate solution or potassium silicate solution.
28. The process of claim 22 , wherein the concentration of said aqueous silicate solution is 20-50% by weight.
29. The process of claim 22 , wherein said silica sol is adjusted to a pH of between 10 and 12.
30. The process of claim 22 , wherein water is removed by means of a process selected from the group consisting of distillation, membrane separation, extraction, and use of a molecular sieve.