CN103087552B - Preparation method of organic nanometer titanium dioxide by means of reversed-phase microemulsion method - Google Patents
Preparation method of organic nanometer titanium dioxide by means of reversed-phase microemulsion method Download PDFInfo
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- CN103087552B CN103087552B CN201310008306.7A CN201310008306A CN103087552B CN 103087552 B CN103087552 B CN 103087552B CN 201310008306 A CN201310008306 A CN 201310008306A CN 103087552 B CN103087552 B CN 103087552B
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Abstract
The invention discloses a preparation method of organic nanometer titanium dioxide by means of a reversed-phase microemulsion method. The method comprises the following steps of: uniformly mixing hexadecyl trimethyl ammonium bromide, acrylic acid and an acrylic ester monomer at the room temperature, dropwise adding de-ionized water to enable the system to be clear, simultaneously adding butyl titanate and a silane coupling agent into the reversed-phase microemulsion system, controlling the adding speed at 0.4-0.6g/min, and stirring the resulting solution for 6-24h at the room temperature to prepare the organic nanometer titanium dioxide. Not only has the preparation method disclosed by the invention the characteristics of simpliness of process, mild reaction condition and the like, but also the prepared organic nanometer titanium dioxide is uniformly dispersed in the reversed-phase microemulsion system which takes the acrylic ester monomer as an oil phase, and can be directly added into water to carry out pre-emulsification and emulsion polymerization to effectively prevent nanometer titanium dioxide aggregation in the posttreatment process and in the redispersion process, and thus the preparation method has a wide application prospect.
Description
Technical field
The invention belongs to inorganic nano-particle field, particularly reverse microemulsion process is prepared the nano titanium oxide (TiO that organises
2) method.
Technical background
Nano titanium oxide (nano-TiO
2) except having small-size effect, surface and interface effect, quantum size effect and macro quanta tunnel effect, also there is unique colour effect, photocatalysis and the specific function such as ultraviolet shielded, have application prospect very widely in fields such as automotive industry, makeup, wastewater treatment, purifying airs.
But, because the specific surface area of nano titanium oxide is large, surface can be high, in non-thermodynamics steady state, therefore very easily reunite, and also have great amount of hydroxy group from the teeth outwards and present wetting ability, be difficult to be dispersed in organic medium, thereby become the Main Bottleneck of its application.Although, by n-TiO
2carry out physical adsorption, coated modification and surface chemical modification, make its surface by inorganic materials or Coated with Organic Matter, can reduce to a certain extent agglomeration, improve the consistency with organic polymer.But these methods normally adopt commercially available nano-TiO
2carry out modification, need first by nano-TiO
2reunite preventing with solvent high speed dispersion, then carry out modification, after modification completes, also have aftertreatment and redispersion process, therefore complex process, cost is higher.
Summary of the invention
The object of the invention is to overcome that existing complex process in nano-titanium dioxide modified and application process, condition control difficulty are large, high in cost of production shortcoming, the method that provides the preparation of a kind of technique is simple and reaction conditions is gentle reverse microemulsion process to organise nano titanium oxide, the prepared nano titanium oxide that organises is dispersed in the Reverse Microemulsion System take acrylate monomer as oil phase, can directly be added to the water and carry out pre-emulsification and letex polymerization.
The present invention, in the mixed solution of acrylate monomer (Acr), vinylformic acid and a small amount of deionized water, by the emulsifying effect of cetyl trimethylammonium bromide (CTAB), forms Reverse Microemulsion System; Then, add in Reverse Microemulsion System by butyl (tetra) titanate with containing the silane coupling agent of alkoxyl group and the two keys of C=C, butyl (tetra) titanate generates nano titanium oxide through hydrolysis, utilize the hydroxyl of silane coupling agent hydrolysis generation and the hydroxyl generation condensation reaction on nano titanium oxide surface simultaneously, make the nano titanium oxide that organises.
Object of the present invention is achieved through the following technical solutions:
Reverse microemulsion process is prepared the method for the nano titanium oxide that organises: at room temperature, in mass fraction, 4-10 part cetyl trimethylammonium bromide (CTAB), 6-14 part vinylformic acid (AA) and 10-30 part acrylate monomer (Acr) are mixed, drip deionized water and make system become clarification, obtain CTAB/AA/Acr/H
2o Reverse Microemulsion System; 2-6 part butyl (tetra) titanate and 1-4 part silane coupling agent are added to CTAB/AA/Acr/H simultaneously
2in O Reverse Microemulsion System, it is 0.4-0.6g/min that control adds speed, then at room temperature stirs 6-24h, makes the nano titanium oxide that organises; Described acrylate monomer is one or both in methyl methacrylate (MMA), butyl acrylate (BA), vinylbenzene (St); Described silane coupling agent is γ-methacryloxypropyl trimethoxy silane (A-174), vinyltrimethoxy silane (A-171) or vinyltriethoxysilane (A-151).
For further realizing the object of the invention, in mass fraction, described deionized water is preferably 10-20 part.In mass fraction, described butyl (tetra) titanate is preferably 3-5 part.
The present invention is at room temperature, and CTAB, AA and acrylate monomer (Acr) are mixed, and drips deionized water and makes system become clarification, obtains CTAB/AA/Acr/H
2o Reverse Microemulsion System; Add in Reverse Microemulsion System by butyl (tetra) titanate with containing the silane coupling agent of alkoxyl group and the two keys of C=C, it is 0.4-0.6g/min that control adds speed, then at room temperature stirs 6-24h, makes the nano titanium oxide that organises simultaneously.
Reverse microemulsion process of the present invention is prepared the method for the nano titanium oxide that organises compared with current techniques, and tool has the following advantages:
(1), due to take acrylate monomer as dispersion medium, therefore the prepared nano titanium oxide system that organises can directly be carried out pre-emulsification and letex polymerization by adding water, easy to use.
(2) when butyl (tetra) titanate hydrolysis generates nano titanium oxide, adopt silane coupling agent directly to its modification, lipophilicity improves, and be conducive to the raising of itself and polymer phase capacitive, and technique is simple, reaction conditions gentleness.
(3) by " bridge formation " effect of silane coupling agent, on nano titanium oxide, introduce the two keys of undersaturated C=C, expand its range of application.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum that reverse microemulsion process is prepared the nano titanium oxide that organises.
Fig. 2 is the transmission electron microscope picture that reverse microemulsion process is prepared the nano titanium oxide that organises.
Embodiment
Below in conjunction with drawings and Examples, the present invention is further illustrated, but embodiments of the present invention are not limit so.
Embodiment 1
At room temperature, 6g CTAB, 9g AA and 24g MMA are mixed, more slowly drip 10g deionized water and make system become clarification, obtain CTAB/AA/MMA/H
2o Reverse Microemulsion System; 4g butyl (tetra) titanate and 1g A-174 are added in Reverse Microemulsion System simultaneously, and it is 0.4-0.6g/min that control adds speed, then at room temperature stirs 24h, and nano titanium oxide must organise.
Fig. 1 is the infrared spectrum that the present embodiment reverse microemulsion process is prepared the nano titanium oxide that organises.Sample preparation and test procedure: the nano titanium oxide system that will organise joins in aqueous ethanolic solution, (Anting Scientific Instrument Factory, Shanghai in whizzer, 800B) with the centrifugal 30min of speed of 3500rpm/min, remove free silane coupling agent, CTAB and acrylate monomer, repeated washing 3 times, then be placed in the baking oven of 45 ℃ and dry.Use pellet technique sample preparation, adopt infrared spectrometer (German Bruker company, Tensor 27) test, wave-number range is 400-4000cm
-1, resolving power is 4cm
-1, scanning times is 16 times.As can be seen from Figure 1,400-900cm
-1in scope, there is the stretching vibration absorption peak of Ti-O, 3250cm
-1place is the O-H stretching vibration peak of titanium dioxide surface, 1630cm
-1and 1400cm
-1place is for being adsorbed in the flexural vibration absorption peak of titanium dioxide surface water, 1500cm
-1and 1430cm
-1place is CH in remaining Surfactant CTAB
2and CH
3vibration absorption peak.1725cm
-1place is the symmetric vibration absorption peak of carbonyl in A-174.At 1170cm
-1there is Ti-O-Si key stretching vibration peak in place, this shows that A-174 is after hydrolysis, with TiO
2the hydroxyl generation dehydration reaction of particle surface generates covalent linkage, is successfully grafted to the surface of nano titanium oxide.
Fig. 2 is the transmission electron microscope picture that reverse microemulsion process is prepared the nano titanium oxide that organises.Sample preparation and test procedure: approximately 500 times of the nano titanium oxide system that will organise dilute with waters, after ultrasonic dispersion, drip on copper mesh, to do when not dry until it, with the phospho-wolframic acid dyeing of 1.5wt%, after drying at room temperature, adopt transmission electron microscope (Dutch FEI electron optics company limited, TECNAIG2-12) to observe the form of modified nano-titanium dioxide.In Fig. 2, the microballoon of black is nano titanium oxide, and median size is in about 10.2nm, and is uniformly dispersed, the agglomeration between particle be improved significantly.
Embodiment 2
At room temperature, 7g CTAB, 7g AA and 30g butyl acrylate (BA) are mixed, more slowly drip 8g deionized water and make system become clarification, obtain CTAB/AA/BA/H
2o Reverse Microemulsion System; 6g butyl (tetra) titanate and 3g A-171 are added in Reverse Microemulsion System simultaneously, and it is 0.4-0.6g/min that control adds speed, then at room temperature stirs 6h, and nano titanium oxide must organise.
Embodiment 3
At room temperature, 8g CTAB, 10g AA and 10g methyl methacrylate, 16g butyl acrylate are mixed, more slowly drip 12g deionized water and make system become clarification, obtain CTAB/AA/MMA-BA/H
2o Reverse Microemulsion System; 5g butyl (tetra) titanate and 4g A-151 are added in Reverse Microemulsion System simultaneously, and it is 0.4-0.6g/min that control adds speed, then at room temperature stirs 12h, and nano titanium oxide must organise.
Embodiment 4
At room temperature, 6g CTAB, 10g AA and 25g methyl methacrylate, 5g vinylbenzene (St) are mixed, more slowly drip 15g deionized water and make system become clarification, obtain CTAB/AA/MMA-St/H
2o Reverse Microemulsion System; 3g butyl (tetra) titanate and 2g A-174 are added in Reverse Microemulsion System simultaneously, and it is 0.4-0.6g/min that control adds speed, then at room temperature stirs 24h, and nano titanium oxide must organise.
Substantially same Fig. 1 of infrared spectrum of prepared by embodiment 2-4 organise nano titanium oxide; Substantially same Fig. 2 of transmission electron microscope picture of the nano titanium oxide that organises of preparation, the particle diameter of what each embodiment was prepared organise nano titanium oxide is as shown in table 1.As can be seen from Table 1, organise in the particle diameter of the nano titanium oxide scope in 9-14.5nm, the graft reaction at titanium dioxide surface by silane coupling agent be described, make surface properties from inorganic become organic, effectively suppressed the generation of agglomeration, system has satisfactory stability.
Table 1
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Particle diameter (nm) | 10.2 | 12 | 9 | 14.5 |
Claims (3)
1. reverse microemulsion process is prepared the method for the nano titanium oxide that organises, it is characterized in that: at room temperature, in mass fraction, by 4 ?10 parts of cetyl trimethylammonium bromides, 6 ?14 parts of vinylformic acid and 10 ?30 parts of acrylate monomers mix, drip deionized water and make system become clarification, obtain CTAB/AA/Acr/H2O Reverse Microemulsion System; By 2 ?6 parts of butyl (tetra) titanates and 1 ?4 parts of silane coupling agents add in CTAB/AA/Acr/H2O Reverse Microemulsion System simultaneously, control add speed be 0.4 ?0.6g/min, then at room temperature stir 6 ?24h, make the nano titanium oxide that organises; Described acrylate monomer is methyl methacrylate and/or butyl acrylate; Described silane coupling agent Wei γ ?methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane or vinyltriethoxysilane.
2. the method for silane coupler modified nano titanic oxide sol according to claim 1, is characterized in that: in mass fraction, described deionized water be 10 ?20 parts.
3. the method for silane coupler modified nano titanic oxide sol according to claim 1, is characterized in that: in mass fraction, described butyl (tetra) titanate be 3 ?5 parts.
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Application publication date: 20130508 Assignee: FOSHAN XINXIANGXING CHEMICAL CO.,LTD. Assignor: South China University of Technology Contract record no.: 2015440000122 Denomination of invention: Preparation method of organic nanometer titanium dioxide by means of reversed-phase microemulsion method Granted publication date: 20140702 License type: Exclusive License Record date: 20150508 |
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