Suspensions of surface treated titanium (IV) oxides and processes for making them
View Patent ↗The disclosure relates to a process for making a surface treated suspension of finely divided titanium (IV) oxide particles, typically, finely divided titanium (IV) oxide nanoparticles, comprising: vigorously mixing (a) a volume of a first component comprising a major proportion of alcohol, a minor proportion of titanium alkoxide and a minor proportion of a titanium alkoxide activator selected from the group consisting of water and a first aqueous base, and b) a volume of a second component selected from the group consisting of water and a second aqueous base, at least one of the first component or the second component having a base therein, the second component being substantially free of alcohol, to form a mixture comprising a suspension of finely divided titanium (IV) oxide particle, the mixture having a water to titanium molar ratio ranging from about 40 to about 1 to about 5000 to about 1, wherein the proportion of the titanium alkoxide, the proportion of the activator, the mixing vigor, and the ratio of the volume of the first component to the volume of the second component are effective for the suspension of the finely divided particles to form in the mixture; and treating the suspension with a compound comprising a source of silicon, aluminum or zinc, and products made by the foregoing process. The suspension can be dried to recover a powder.
1. A single step process for making a nanoparticle suspension of titanium (IV) oxide particles using a high water to titanium molar ratio, comprising the following steps:
1) mixing with a vigor equivalent to a shear rate of greater than 100 s −1 (a) and (b) wherein
(a) is a volume of a first component comprising an alcohol in an amount of more than 50 wt. % based on the weight of the first component, a titanium alkoxide in an amount ranging from 0.001 wt. % to 6 wt. % based on the weight of the first component, and a titanium alkoxide activator in an amount ranging from 0.2 wt. % to 1.6 wt. % based on the weight of the first component, the titanium alkoxide activator being selected from the group consisting of water and a first aqueous base selected from the group consisting of ammonium hydroxide, sodium hydroxide, sodium pyrophosphate, potassium pyrophosphate, sodium citrate, diammonium hydrogen phosphate and mixtures thereof, and
(b) is a volume of a second component selected from the group consisting of water and a second aqueous base selected from the group consisting of ammonium hydroxide, sodium hydroxide, sodium pyrophosphate, potassium pyrophosphate, sodium citrate, diammonium hydrogen phosphate and mixtures thereof,
at least one of the first component or the second component having a base therein,
2) rapidly forming a mixture comprising a suspension of titanium (IV) oxide nanoparticles having a volume-weighted median particle size measured via dynamic light scattering below approximately 100 nm, the mixture having a water to titanium molar ratio ranging from about 40 to about 1 to about 5000 to about 1, and
3) treating the suspension of titanium (IV) oxide nanoparticles with a source of silicon, aluminum or zinc.
2. The process of claim 1 in which the source of silicon is tetraethyl ortho silicate or a silane having the formula:
R X Si(R′) 4-x
wherein
R is a nonhydrolyzable aliphatic, cycloaliphatic or aromatic group having at least 1 to about 20 carbon atoms;
R′ is a hydrolyzable group such as an alkoxy, halogen, acetoxy or hydroxy or mixtures thereof; and
x=1 to 3.
3. The process of claim 1 in which the source of aluminum is triethoxy aluminum.
4. The process of claim 1 in which the source of zinc is zinc 2-methoxy ethoxide.
5. The process of claim 1 in which the ratio of the volume of the first component to the volume of the second component is about 1 to about 1 to about 9 to about 1.
6. The process of claim 1 in which the titanium alkoxide is selected from the group consisting of titanium (IV) isopropoxide, titanium (IV) n-butoxide, titanium (IV) methoxide, titanium (IV) ethoxide, and titanium (IV) n-propoxide and mixtures thereof.
7. The process of claim 1 in which the alcohol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and butanediol and mixtures thereof.
8. The process of claim 1 further comprising drying the mixture to recover a surface treated powder.
9. The process of claim 1 in which the mixing is accomplished in a homogenizer wherein the rotor speed is greater than about 500 rpm.
10. The process of claim 1 in which the base of the second aqueous base is in a concentration ranging from about 0.001 M to about 0.030 M in the second component.
11. The process of claim 1 in which the base of the second aqueous base is ammonium hydroxide in a concentration ranging from about 0.006 M to about 14.8 M in the second component.
12. The process of claim 1 , wherein steps 2) and 3) occur at ambient temperatures.
13. The process of claim 1 , wherein the second component is substantially free of alcohol.