CN102702798B - Modified silica filler and preparation method thereof - Google Patents
Modified silica filler and preparation method thereof Download PDFInfo
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- CN102702798B CN102702798B CN201210199731.4A CN201210199731A CN102702798B CN 102702798 B CN102702798 B CN 102702798B CN 201210199731 A CN201210199731 A CN 201210199731A CN 102702798 B CN102702798 B CN 102702798B
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Abstract
The invention relates to modified silica filler and a preparation method thereof, in particular to the silica filler with the surface on which amphoteric surfactants are modified, and the preparation method for the silica filler, and belongs to the technical field of preparation of novel functional materials. The method comprises the following steps of: adding 1 mass part of triethylamine, 100 mass parts of tetrahydrofuran, 10 mass parts of superfine silica, 0.2 to 1 part of 2-bromoisobutyryl bromide into a reaction container, sealing, reacting with stirring at room temperature for 16 hours, filtering, washing, and drying to obtain activated silica; and dissolving 2 to 10 mass parts of methylacryloyl oxy modified betaine in 100 mass parts of mixed solution of methanol and water, adding 10 mass parts of activated silica, introducing argon and stirring, adding 0.05 mass part of mixture of bipyridine and cuprous bromide, continuously introducing argon and stirring, after reaction, washing reactant by using deionized water, filtering and drying to obtain the modified silica filler. The preparation process is simple, and the filler is high in performance, wide in application range and good in using effect.
Description
Technical field:
The present invention relates to a kind of improved silica filler and preparation method thereof, particularly a kind of finishing has silica filler of amphoterics and preparation method thereof, belongs to new function material preparing technical field.
Background technology:
Superfine silicon dioxide (White Carbon black) is one of important filler of the goods such as rubber, plastics, coating, cosmetics of everyday use with its superior stability, reinforcement, thickening property and thixotropy etc. always.Superfine silicon dioxide has very large specific surface area and very strong adsorptive power, contains a large amount of silicon hydroxyls (Si-OH) have certain chemical reactivity because of its surface simultaneously.Therefore, using superfine silicon dioxide as carrier, carry out physics or chemical modification and prepare functional stuffing and caused extensive concern and attention, and antibacterial filler is most important Yi Ge branch wherein.At present, take the anti-biotic material that silicon-dioxide is carrier mainly prepares by silver or silver ions modification of ultrafine silicon dioxide.As patent CN1308868 discloses a kind of preparation method of inorganic broad-spectrum antimicrobial additive, by silicon-dioxide and silver nitrate solution and NaOH solution effects, by method dry, that inorganic broad-spectrum antimicrobial additive is prepared in calcination; Patent CN1308866 discloses a kind of preparation method of inorganic broad-spectrum antimicrobial additive, by silicon-dioxide and Ag
+, Cu
2+, Zn
2+, Ni
2+, Co
2+the aqueous solution forming reacts, more after filtration, dry and produce the method for inorganic broad-spectrum antimicrobial additive; Patent CN1615698 discloses a kind of complex antimicrobials, is to be mixed, calcine, grind and obtained by silver carbonate, zinc oxide, silicon-dioxide; Patent CN101889582A discloses a kind of novel multifunctional nano-assembly inorganic antibacterial agent and preparation method thereof, be silicon-dioxide or the nano silicon with nano aperture be carrier, the antibacterial components such as assembling silver, copper, zinc in the nanometer micropore of carrier and having concurrently of obtaining is antibacterial, the multifunctional inorganic antiseptic-germicide product of mildew-resistant, anti-algae effect; Patent CN101912634A discloses a kind of preparation method of the antibacterial biological dressing containing nanometer silver/nano silicon, in Polyvinyl acetal reaction, add chitosan/polyvinyl alcohol blended liquid and carry silver-colored SiO 2 powder, making the antibacterial biological dressing containing nanometer silver/nano silicon.This class material carries out sterilization, antibacterial by silver or silver ions, but due to easy oxidized the losing activity of silver, simultaneously as precious metal, the cost of silver-colored sterilant is comparatively expensive, and this has limited its range of application.Outside desilver, other mineral compound also can carry out physically modified with silicon-dioxide and prepare anti-biotic material, as patent CN1883270 discloses the making method of a kind of Cadmium Sulfide, silicon-dioxide complex antimicrobials, this product can kill bacterium, the fungi touching under the effect of light, and by itrogenous organic substance, the obnoxious flavoures such as organic phosphorous insecticide are decomposed into harmless small-molecule substance.But the toxicity of Cadmium Sulfide is stronger, is not only detrimental to health, also can cause disadvantageous effect to environment.
Except aforesaid method, adopt organic antibacterial agent to carry out chemical modification to silicon-dioxide and also can be used for preparing anti-biotic material, as patent CN101796961A discloses a kind of silicon-dioxide-curcumine and derivative hybrid material and preparation method, this material forms by amino silicane coupling agent and silicon-dioxide grafting by having bioactive curcumine or derivatives thereof.But curcumine poor stability, inefficient shortcoming need to solve.
Betaine type amphoteric surfac-tant's molecule is comprised of with positively charged polar portion together with electronegative nonpolar part, polar portion is quaternary ammonium cations and carboxylate radical or sulfonate radical negative ion, it not only has goodish bactericidal mould proof effect, excellent anti-protein adsorption effect, and to people and biological almost non-toxic.For example patent CN102040742A discloses a kind of surfacing with anti-protein adsorption character and preparation method thereof, by having the monomer molecule of double ion character, in the graft polymerization of organosilicon matrix surface, prepares, can blocks protein in the absorption of material surface.Yet, utilize and through the trimethyl-glycine of methacryloxy modification and silicon-dioxide, to carry out chemical reaction and prepare the silica filler of antibacterial, anti-protein adsorption excellent property and there is not yet report.
Summary of the invention:
The object of the invention is to overcome the shortcoming that prior art exists, reinforcement, thickening property and thixotropy for silicon-dioxide excellence, and good antibacterial of betaine type amphoteric surfac-tant, the feature of anti-protein adsorption and safety and environmental protection, the trimethyl-glycine by methacryloxy modification combines both at superfine silicon dioxide surface grafting polymerization, and preparation is a kind of has a superfine silicon dioxide filler antibacterial, anti-protein adsorption.
To achieve these goals, the improved silica filler that the present invention proposes is that the trimethyl-glycine by methacryloxy modification is prepared from superfine silicon dioxide surface grafting polymerization, and its molecular structural formula is:
In formula, R
1for the groups such as methyl, ethyl, phenyl, substituted-phenyl, R
2for having the organic group of double ion character, n is the natural number of > 0.
The preparation technology of silica filler of the present invention comprises the following steps:
(1) in reaction vessel, add 1 mass parts triethylamine, 100 mass parts tetrahydrofuran (THF)s, 10 mass parts superfine silicon dioxides, 0.2-1 mass parts 2-bromo isobutyl acylbromide, normal-temperature reaction 16h is stirred in sealing, after filtration, washing, the dry silicon-dioxide that can obtain activation;
(2) by the trimethyl-glycine of 2-10 mass parts methacryloxy modification, be dissolved in the mixing solutions that 100 mass parts methyl alcohol and water volume ratio are 3:1, the silicon-dioxide that adds 10 mass parts activation, logical argon gas stirs after 10min, add the mixture that 0.05 mass parts second bipyridine and cuprous bromide mol ratio are 1:1, continue logical argon gas and stir 24 hours, after reaction finishes, with deionized water rinsing reactant filtration, after being dried, obtain superfine modified silica filler.
The superfine silicon dioxide the present invention relates to comprises silicon-dioxide prepared by vapor phase process, silicon-dioxide prepared by the precipitator method and the silicon-dioxide of hydrophobic treatment; The specific surface area of superfine silicon dioxide is 50-200m
2/ g.
The trimethyl-glycine of the methacryloxy modification the present invention relates to comprises the sulphonic acid betaine of methacryloxy modification and the carboxylic acid trimethyl-glycine of methacryloxy modification.
The present invention compared with prior art, prepares at superfine silicon dioxide surface grafting polymerization by the trimethyl-glycine of methacryloxy modification that silica filler has reinforced silicon dioxide and trimethyl-glycine is antibacterial and the character of anti-protein adsorption; The anti-fouling material that this filler and silicone resin are mixed with, in laboratory, diatom adheres to experiment and shows to have good mariner growth prevent adhewsive action; Its preparation technology is simple, and the carrier performance of preparation is good, and range of application is large, and result of use is good.
Embodiment:
Below by embodiment, the invention will be further described.
Embodiment 1:
The present embodiment adds 1 mass parts triethylamine in reaction vessel, 100 mass parts tetrahydrofuran (THF)s, 10 mass parts superfine silicon dioxides (Degussa gas-phase silica AerosilOX50, specific surface area 50m
2/ g), 0.2 mass parts 2-bromo isobutyl acylbromide, normal-temperature reaction 16h is stirred in sealing, after filtration, washing, the dry silicon-dioxide that obtains activation; Again by the sulphonic acid betaine (N of 2 mass parts methacryloxy modifications, N-dimethyl-methylacryoyloxyethyl-aminopropanesulfonic acid inner salt) be dissolved in the mixing solutions (volume ratio is 3:1) of 100 mass parts methyl alcohol and water, the silicon-dioxide that adds again 10 mass parts activation, logical argon gas stirs after 10min, the mixture (mol ratio is 1:1) that adds 0.05 mass parts second bipyridine and cuprous bromide, continuing logical argon gas stirs 24 hours, after reaction finishes, with deionized water rinsing reactant and after filtering and being dried, make modification of ultrafine silicon dioxide filler.
Embodiment 2:
The present embodiment adds 1 mass parts triethylamine in reaction vessel, 100 mass parts tetrahydrofuran (THF)s, 10 mass parts superfine silicon dioxides (Cabot hydrophobic type gas phase White Carbon black Cab-o-silTS530, specific surface area 200m
2/ g), 1 mass parts 2-bromo isobutyl acylbromide, normal-temperature reaction 16h is stirred in sealing, after filtration, washing and the dry silicon-dioxide that makes activation; Again by the carboxylic acid trimethyl-glycine (2-(N of 10 mass parts methacryloxy modifications, N '-dimethylamino) ethylacrylic acid methyl esters) be dissolved in the mixing solutions (volume ratio is 3:1) of 100 mass parts methyl alcohol and water, the silicon-dioxide that adds 10 mass parts activation, logical argon gas stirs after 10min, the mixture (mol ratio is 1:1) that adds 0.05 mass parts second bipyridine and cuprous bromide, continuing logical argon gas stirs 24 hours, after reaction finishes, with deionized water rinsing reactant filtration, after being dried, obtain modification of ultrafine silicon dioxide filler.
Embodiment 3:
The present embodiment adds 1 mass parts triethylamine in reaction vessel, 100 mass parts tetrahydrofuran (THF)s, 10 mass parts superfine silicon dioxides (Degussa hydrophobic type deposition white carbon black Sipernat D10, specific surface area 90m
2/ g), 0.5 mass parts 2-bromo isobutyl acylbromide, normal-temperature reaction 16h is stirred in sealing, after filtration, washing and the dry silicon-dioxide that makes activation; Again by the sulfonic acid acid trimethyl-glycine (N of 5 mass parts methacryloxy modifications, N-dimethyl-methylacryoyloxyethyl-aminopropanesulfonic acid inner salt) be dissolved in the mixing solutions (volume ratio is 3:1) of 100 mass parts methyl alcohol and water, the silicon-dioxide that adds 10 mass parts activation, logical argon gas stirs after 10min, the mixture (mol ratio is 1:1) that adds 0.05 mass parts second bipyridine and cuprous bromide, continuing logical argon gas stirs 24 hours, after reaction finishes, with deionized water rinsing reactant filtration, after being dried, obtain modification of ultrafine silicon dioxide filler.
Embodiment 4:
The present embodiment mixes the prepared improved silica filler of embodiment 3 as new base glue by the mass ratio of 1:20 with the base glue (Base agent) of liquid silastic (DOW CORNING T2 glue), add again 10% curing component (Curing agent) to mix, on slide glass, ambient cure is 72 hours, preparation experiment print; Again experiment print and T2 glue print being put into diatom concentration is 1 * 10
5in the nutrient solution of individual/ml, cultivate adhesion condition the counting of after 3 hours, examining under a microscope print surface diatom, result shows that the inhibiting rate that experiment print adheres to diatom has improved 32.7% compared with T2 glue print.
Claims (2)
1. a preparation method for improved silica filler, is characterized in that comprising the following steps:
(1) in reaction vessel, add 1 mass parts triethylamine, 100 mass parts tetrahydrofuran (THF)s, 10 mass parts superfine silicon dioxides, 0.2-1 mass parts 2-bromo isobutyl acylbromide, normal-temperature reaction 16h is stirred in sealing, after filtration, wash and be drying to obtain the silicon-dioxide of activation;
(2) by the trimethyl-glycine of 2-10 mass parts methacryloxy modification, be dissolved in the mixing solutions that 100 mass parts methyl alcohol and water volume ratio are 3:1, the silicon-dioxide that adds 10 mass parts activation, logical argon gas stirs after 10min, add the mixture that 0.05 mass parts second bipyridine and cuprous bromide mol ratio are 1:1, continue to lead to argon gas and stir 24 hours, after reaction finishes, with deionized water rinsing reactant and after filtering and being dried, obtain superfine modified silica filler.
2. the preparation method of improved silica filler according to claim 1, is characterized in that silicon-dioxide that the superfine silicon dioxide relating to comprises vapor phase process and prepare, silicon-dioxide prepared by the precipitator method and the silicon-dioxide of hydrophobic treatment; The specific surface area of superfine silicon dioxide is 50-200m
2/ g; The trimethyl-glycine of the methacryloxy modification relating to comprises the sulphonic acid betaine of methacryloxy modification and the carboxylic acid trimethyl-glycine of methacryloxy modification.
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| CN201210199731.4A CN102702798B (en) | 2012-06-18 | 2012-06-18 | Modified silica filler and preparation method thereof |
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| CN201210199731.4A CN102702798B (en) | 2012-06-18 | 2012-06-18 | Modified silica filler and preparation method thereof |
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| CN102702798B true CN102702798B (en) | 2014-04-02 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846354A (en) * | 2015-05-12 | 2015-08-19 | 中国船舶重工集团公司第七二五研究所 | Antifouling and antibacterial treatment method for titanium and titanium alloy surface |
| CN105622870B (en) * | 2016-03-11 | 2018-01-23 | 中国船舶重工集团公司第七二五研究所 | A kind of sulfate reducing bacteria corrosion suppresses the preparation method of film |
| WO2020256340A2 (en) * | 2019-06-21 | 2020-12-24 | 고려대학교산학협력단 | In vivo bulking agent, injection comprising same, and preparation method therefor |
| CN110981211B (en) * | 2019-12-31 | 2022-08-12 | 江苏盈天化学有限公司 | Preparation method of polymer modified glass filler for rectification |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2155407A1 (en) * | 1993-02-12 | 1994-08-18 | David M. Regan | Surface modified silica |
| WO1996039821A1 (en) * | 1995-06-07 | 1996-12-19 | Bsi Corporation | Virus inactivating coatings |
| US6146688A (en) * | 1997-12-23 | 2000-11-14 | Morgan; Harry C. | Method of creating a biostatic agent using interpenetrating network polymers |
| FR2900410B1 (en) * | 2006-04-27 | 2008-08-29 | Coatex Sas | PROCESS FOR TREATING TALC WITH AMPHOTERIC POLYMERS, TALC OBTAINED, USE OF SAID TALC AS A REDUCING AGENT OF THE QUANTITY OF COLLOIDS IN THE MANUFACTURE OF AQUEOUS SYSTEMS. |
| CN101891867A (en) * | 2010-04-30 | 2010-11-24 | 中国科学院长春应用化学研究所 | Method for preparing SiO2-poly(dimethylaminoethyl methacrylate) (PDMAEMA) nanoparticles having core-shell structure |
| CN102040742A (en) * | 2010-10-23 | 2011-05-04 | 中国船舶重工集团公司第七二五研究所 | Surface material with protein adsorption resistant property and preparation method thereof |
| CN102181175A (en) * | 2011-03-23 | 2011-09-14 | 吴江友鑫高分子材料科技有限公司 | Preparation method of surface modified nano particles and application of product thereof |
-
2012
- 2012-06-18 CN CN201210199731.4A patent/CN102702798B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2155407A1 (en) * | 1993-02-12 | 1994-08-18 | David M. Regan | Surface modified silica |
| WO1996039821A1 (en) * | 1995-06-07 | 1996-12-19 | Bsi Corporation | Virus inactivating coatings |
| US6146688A (en) * | 1997-12-23 | 2000-11-14 | Morgan; Harry C. | Method of creating a biostatic agent using interpenetrating network polymers |
| FR2900410B1 (en) * | 2006-04-27 | 2008-08-29 | Coatex Sas | PROCESS FOR TREATING TALC WITH AMPHOTERIC POLYMERS, TALC OBTAINED, USE OF SAID TALC AS A REDUCING AGENT OF THE QUANTITY OF COLLOIDS IN THE MANUFACTURE OF AQUEOUS SYSTEMS. |
| CN101891867A (en) * | 2010-04-30 | 2010-11-24 | 中国科学院长春应用化学研究所 | Method for preparing SiO2-poly(dimethylaminoethyl methacrylate) (PDMAEMA) nanoparticles having core-shell structure |
| CN102040742A (en) * | 2010-10-23 | 2011-05-04 | 中国船舶重工集团公司第七二五研究所 | Surface material with protein adsorption resistant property and preparation method thereof |
| CN102181175A (en) * | 2011-03-23 | 2011-09-14 | 吴江友鑫高分子材料科技有限公司 | Preparation method of surface modified nano particles and application of product thereof |
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