CN103395790B - Esterification Nano-meter SiO_2 2the preparation method of hydroxy acrylate organic dispersions - Google Patents
Esterification Nano-meter SiO_2 2the preparation method of hydroxy acrylate organic dispersions Download PDFInfo
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Abstract
The present invention relates to coating processing technique field, specifically a kind of esterification Nano-meter SiO_2
2the preparation method of hydroxy acrylate organic dispersions.This preparation method take water glass as raw material, with the solvent of water, take hydroxy acrylate as esterifying agent, by the technique of dissolving, filtration, acidifying, esterification dehydration, filtration desalination, obtains surface esterification modified Nano SiO
2hydroxy acrylate organic dispersions.The surface esterification modified Nano SiO obtained by the method
2hydroxy acrylate organic dispersions, the reaction monomers can be polymerized as resin solution, in Raolical polymerizable process, by Nano-meter SiO_2
2be introduced directly into the polymer segment of reaction system, can Nano-meter SiO_2 be realized
2stable, high level, nano-dispersed truly.
Description
Technical field
The present invention relates to coating processing technique field, specifically relate to a kind of by Nano-meter SiO_2
2be incorporated into a kind of esterification Nano-meter SiO_2 in vinylformic acid (ester) resin system
2the preparation method of hydroxy acrylate organic dispersions.
Background technology
Nano-meter SiO_2
2introducing effectively can improve hardness, the scoring resistance of organic polymer resin film, the transparency of film can be kept simultaneously.Main employing powder nanometer SiO at present
2the method of modify polymeric resins, although by organo silane coupling agent process powder nanometer SiO
2surface, powder nanometer SiO
2cannot avoid the reunion of chemistry and physics, the nano level being difficult to during use reach truly is dispersed, and thus nano effect and function are difficult to fully manifest.
" the Nano-meter SiO_2 that tradition uses
2" or powder or " silicon sol " of water-dispersible form." the Nano-meter SiO_2 of powder
2" in resin system dispersion bring the inconvenience of use, even if importantly carry out organic modification (as organic-silicon-modified) to its surface, increase its consistency with organic system, also very difficult by the " Nano-meter SiO_2 of powder
2" be dispersed in polymeric system with " nanoscale ", produce the practical problems of poor storage stability.And the colloidal sol type " Nano-meter SiO_2 of water-dispersible form
2", require strict (more than pH8 stablizes) environment pH, surface cannot realize " hydrophobic " modification simultaneously, causes " the Nano-meter SiO_2 of colloidal sol type
2" be difficult to be applied in high molecular polymerization objects system (coating, resin).
Surface esterification modified Nano SiO
2hydroxy acrylate organic dispersions has evaded above-mentioned two class " Nano-meter SiO_2
2" drawback, have pH wide ranges, good oil soluble, as the one of the reaction raw materials of radical polymerization, make " Nano-meter SiO_2
2" with the form of chemical bonding be incorporated in acrylic resin segment provide a kind of may.9th phases in 2012 of " plating and decoration ", " synthesis of nano silicon/polyacrylate composite emulsion and film performance thereof ", handsome as etc. report with modified silicasol and acrylic ester monomer in-situ polymerization, employing monomer pre-emulsification, semicontinuous dripping method have prepared high silicon content Nano-meter SiO_2
2a kind of method of/poly acrylate composite emulsion; " Beijing University of Chemical Technology's journal " the 2nd phase in 2005, " high SiO
2the method of the preparation of content silicon sol/poly acrylate composite emulsion ", Chen Shi etc. report a kind of high SiO
2the method of the preparation of content silicon sol/poly acrylate composite emulsion; " electronic component and material " 2010 the 10th phase, " preparations and applicatio of ethylene glycol Nano silica sol ", Ren Zhijun, Chen Yao etc. report a kind of Nano-meter SiO_2
2the preparation method of ethylene glycol organic dispersions, and inquired into application in the electrolytic solution.
For surface esterification modified Nano SiO
2hydroxy acrylate organic dispersions, does not have the report of its structure, preparation technology and application aspect at present.
Summary of the invention
The invention provides a kind of esterification Nano-meter SiO_2
2the preparation method of hydroxy acrylate organic dispersions.This preparation method take water glass as raw material, with the solvent of water, take hydroxy acrylate as esterifying agent, by the technique of dissolving, filtration, acidifying, esterification dehydration, filtration desalination, obtains surface esterification modified Nano SiO
2hydroxy acrylate organic dispersions.
For guaranteeing the processable of water glass, the modulus of water glass is 1.5 ~ 2.5, preferably 2.
When water glass and water prepare sodium silicate aqueous solution, water glass and quality are than being 1:4 ~ 1:8, preferred 1:6.When water glass is less than 1:4 with quality ratio, the viscosity of fluid is excessive, causes the processes such as filtration, desalination to carry out; When water glass is greater than 1:8 with quality ratio, the effective constituent in fluid-water glass content is too low, and production efficiency is low, and yield is low, and product runs off serious with sepn process.
When sodium silicate aqueous solution carries out acidification, acidulant employed is hydrochloric acid; The salt (sodium-chlor) that sodium silicate aqueous solution generates with hydrochloric acid is easily separated, and technique is easy to realize, and other is sour, and as phosphoric acid, nitric acid etc., phosphoric acid salt, nitrate that neutralization generates, be difficult to from system filtering separation.Acidifying pH is 2 ~ 4, Nano-meter SiO_2
2carboxylate is stable in 2 ~ 4 scopes at pH, and exceed this scope, preparation easily occurs hydrolyzate and produces precipitation, and preferred acidifying pH is 3.The concentration of hydrochloric acid is 10% ~ 20%, preferably 15%; In acidization, the concentration of hydrochloric acid is large, and easily cause partial concn too high, local pH is too low, unstable products and hydrolytic precipitation; And the concentration of hydrochloric acid is too low, acidization brings a large amount of water into, easily causes the production concentration of reaction system too low, and production efficiency is low, and yield is low.
Described esterifying agent is at least one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410.
The consumption of described esterifying agent is 2.0 ~ 5.0 times of sodium silicate solid quality, and within the scope of this, the mobility of system is more suitable, preferably 3.5 times.
The temperature of reaction of esterification dehydration is 40 DEG C ~ 80 DEG C, and the organic ester compound relative stability of inorganics is poor, and temperature of reaction is limited in 40 DEG C ~ 80 DEG C can avoid SiO
2precipitation generates; The first low temperature of preferred employing, the temperature of reaction of rear high temperature; More preferably adopt initial reaction temperature to be 50 DEG C, heat up gradually, whole beginning temperature of reaction is the temperature of reaction of 70 DEG C.Esterification dehydration reaction is carried out under the environment of 0.01 ~ 0.03MPa, preferred 0.02Mpa; Vacuum tightness is too low, and water is distilled out of the not thorough of displacement, and vacuum tightness is too high, and the loss of hydroxy acrylate class is serious.
The principle of this preparation method is Nano-meter SiO_2 aqueous solution mesosilicic acid sodium and hydrochloric acid reaction being generated silicic acid and primary condensation multi-silicate aqueous colloidal
2, this Nano-meter SiO_2
2surface cover by numerous-OH, Nano-meter SiO_2
2surface-OH there is higher reactive behavior, can with organic hydroxyl generation esterification, slough water molecules, the Nano-meter SiO_2 formed
2the hydroxyl alkoxy on surface replaces, and finally obtains surface esterification modified Nano SiO
2hydroxy acrylate organic dispersions.
The surface esterification modified Nano SiO obtained by the method
2hydroxy acrylate organic dispersions, the mass percentage of its SiO2 is 10% ~ 25%, its SiO
2mass percentage optimum be 20%, can as resin solution polymerization reaction monomers.In Raolical polymerizable process, by Nano-meter SiO_2
2be introduced directly in the polymer segment of reaction system, realize at " esterification modification Nano-meter SiO_2
2hydroxy acryl acid monomer organic dispersions " in carry out the original position radical polymerization of vinylformic acid (ester) monomer, realize Nano-meter SiO_2
2stable, high level, nano-dispersed truly.Make the film forming properties of acrylic resin paint, be significantly improved in hardness, scoring resistance, wear resistance etc.
Embodiment
Embodiment 1
In 250mL tri-mouthfuls of reaction flasks that stirring, pH meter, thermometer, condenser and vacuum pump are housed, add the water glass 16.5 grams that 100mL pure water and modulus are 2, about 0.5 hour is dissolved under the state stirred, stop stirring, sodium silicate solution is filtered, insoluble or the mechanical impurity filter residue of reject, it is stand-by that filtrate turns back to three mouthfuls of reaction flasks; Under the state stirred, the HCl of 15% is dripped to the filtrate medium in reaction flask, until pH is down to 3, continues stirring after 0.5 hour, in the sodium silicate solution in reaction flask, add the Hydroxyethyl acrylate of 50 grams, under the state stirred, open vacuum pump, vacuum, by condenser, makes the vacuum tightness in reaction flask (absolute pressure) control after about 0.02MPa, start slowly to be warming up to about 50 DEG C, now there are flowing out in condenser.About need 0.5 hour, the temperature in reaction flask rises to 70 DEG C, and the anhydrous outflow of device to be condensed, illustrates SO in proved response
2complete with the reactive esterify hydroxy of Hydroxyethyl acrylate, now under the state stirred, stop heating, remove the vacuum of reaction flask, by reaction mass to going out, after room temperature left undisturbed overnight, suspension liquid supernatant liquid and lower floor being contained NaCl filters and merges, and obtains SO
2content be 20.8%, viscosity is the transparent surface esterification modified Nano SiO of 18MPas
2acrylate hydroxyl ethyl ester dispersion liquid 60.2 grams.Wherein, viscosity measures, SO according to " mensuration of GB/T22235-2008 liquid viscosity "
2content measures according to the mensuration of dioxide-containing silica " in the GB/T18174-2000 rubber ", and following examples adopt identical standard to viscosity, SO
2content measures.
Embodiment 2
In the reaction unit of embodiment 1, add the water glass 25 grams that 100mL pure water and modulus are 2.5, filter after stirring and dissolving, reject filter residue, filtrate turns back in three mouthfuls of reaction flasks, under the state stirred, 10%HCl to pH=2 is dripped to reaction flask, the Rocryl 410 of 50 grams is added again in reaction flask, after stirring, open vacuum pump, vacuum tightness (absolute pressure) in reaction flask is controlled after about 0.01MPa, start slowly to be warming up to about 40 DEG C, in 0.5 hour, temperature in reaction flask is risen to 75 DEG C gradually, device evaporated condensation water to be condensed flows out, stop heating, remove the vacuum of reaction flask, by reaction mass to going out, after room temperature left undisturbed overnight, turbid solution supernatant liquid and lower floor being contained NaCl filters and merges, obtain SO
2content be 24.9%, viscosity is the transparent surface esterification modification Nano-meter SiO_2 of 24.7MPas
2rocryl 410 dispersion liquid 68.1 grams.
Embodiment 3
In the reaction unit of embodiment 1, add the water glass 25 grams that 100mL pure water and modulus are 1.5, filter after stirring and dissolving, reject filter residue, filtrate turns back in three mouthfuls of reaction flasks, under the state stirred, 20%HCl to pH=4 is dripped to reaction flask, the mixture of the Hydroxyethyl acrylate of 50 grams and the hydroxyethyl methylacrylate of 50 grams is added again in reaction flask, after stirring, open vacuum pump, vacuum tightness (absolute pressure) in reaction flask is controlled after about 0.03MPa, start slowly to be warming up to about 50 DEG C, in 0.5 hour, temperature in reaction flask is risen to 80 DEG C gradually, device evaporated condensation water to be condensed flows out, stop heating, remove the vacuum of reaction flask, by reaction mass to going out, after room temperature left undisturbed overnight, turbid solution supernatant liquid and lower floor being contained NaCl filters and merges, obtain SO
2the surface esterification modified Nano SiO that content is 12.5%, viscosity is 7.5MPas
2mixing hydroxy acrylate organic dispersions 118.4 grams.
Embodiment 4
In the reaction unit of embodiment 1, add the water glass 20 grams that 100mL pure water and modulus are 1.5, filter after stirring and dissolving, reject filter residue, filtrate turns back in three mouthfuls of reaction flasks, under the state stirred, 10%HCl to pH=2 is dripped to reaction flask, the mixture of the Rocryl 410 of 70 grams and the hydroxyethyl methylacrylate of 30 grams is added again in reaction flask, after being uniformly mixed, open vacuum pump, vacuum tightness (absolute pressure) in reaction flask is controlled after about 0.01MPa, start slowly to be warming up to about 45 DEG C, in 0.5 hour, temperature in reaction flask is risen to 75 DEG C gradually, device evaporated condensation water to be condensed flows out, stop heating, remove the vacuum of reaction flask, by reaction mass to going out, after room temperature left undisturbed overnight, turbid solution supernatant liquid and lower floor being contained NaCl filters and merges, obtain SO
2the surface esterification modified Nano SiO that content is 10.1%, viscosity is 5.0MPas
2mixing hydroxy acrylate organic dispersions 118.4 grams.
Embodiment 5
In the reaction unit of embodiment 1, add the water glass 13 grams that 100mL pure water and modulus are 2.0, filter after stirring and dissolving, reject filter residue, filtrate returns in three mouthfuls of reaction flasks, under the state stirred, 20%HCl to pH=3 is dripped to reaction flask, the Hydroxyethyl acrylate of 50 grams is added again in reaction flask, after stirring, open vacuum pump, vacuum tightness (absolute pressure) in reaction flask is controlled after about 0.03MPa, start slowly to be warming up to about 50 DEG C, in 0.5 hour, temperature in reaction flask is risen to 80 DEG C gradually, device evaporated condensation water to be condensed flows out, stop heating, remove the vacuum of reaction flask, by reaction mass to going out, after room temperature left undisturbed overnight, turbid solution supernatant liquid and lower floor being contained NaCl filters and merges, obtain SO
2the esterification Nano-meter SiO_2 that content is 14.3%, viscosity is 17.3MPas
2hydroxy acrylate organic dispersions 57.6 grams.
The above embodiment only have expressed some embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. an esterification Nano-meter SiO_2
2the preparation method of hydroxy acrylate organic dispersions, this preparation method take water glass as raw material, with the solvent of water, take hydroxy acrylate as esterifying agent, by the technique of dissolving, filtration, acidifying, esterification dehydration, filtration desalination, obtain surface esterification modified Nano SiO
2hydroxy acrylate organic dispersions, described esterifying agent is at least one in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410.
2. preparation method according to claim 1, is characterized in that: the modulus of described water glass is 1.5 ~ 2.5.
3. preparation method according to claim 2, is characterized in that: when water glass and water prepare sodium silicate aqueous solution, and water glass and quality are than being 1:4 ~ 1:8.
4. preparation method according to claim 3, is characterized in that: when sodium silicate aqueous solution carries out acidification, and acidulant employed is hydrochloric acid, and acidifying pH is 2 ~ 4; The concentration of described hydrochloric acid is 10% ~ 20%.
5. preparation method according to claim 4, is characterized in that: the modulus of described water glass is 2; Water glass and quality are than being 1:6; Acidifying pH is 3; The concentration of described hydrochloric acid is 15%.
6. preparation method according to claim 1, is characterized in that: the consumption of described esterifying agent is 2.0 ~ 5.0 times of sodium silicate solid quality.
7. preparation method according to claim 6, is characterized in that: the temperature of reaction of esterification dehydration is 40 DEG C ~ 80 DEG C.
8. preparation method according to claim 7, is characterized in that: esterification dehydration reaction is carried out under the environment of 0.01 ~ 0.03MPa.
9. preparation method according to claim 8, is characterized in that: the temperature of reaction of esterification dehydration adopts initial reaction temperature to be 50 DEG C, heats up gradually, and whole beginning temperature of reaction is the temperature of reaction of 70 DEG C; The consumption of described esterifying agent is 3.5 times of sodium silicate solid quality; Esterification dehydration reaction is carried out under the environment of 0.02MPa.
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| CN1517411A (en) * | 2003-01-14 | 2004-08-04 | 华东理工大学 | Preparing of dispersed-in-water nono-SIO2 with durable stability at ordinary temp and its hybridized materaial |
| CN101497749A (en) * | 2009-03-06 | 2009-08-05 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
| CN102604006A (en) * | 2012-03-09 | 2012-07-25 | 太原理工大学 | Preparation method for acidic silica sol in-situ modified acrylate emulsion |
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|---|---|---|---|---|
| US20080011687A1 (en) * | 2006-07-17 | 2008-01-17 | Floryan De Campo | Silica scale inhibition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517411A (en) * | 2003-01-14 | 2004-08-04 | 华东理工大学 | Preparing of dispersed-in-water nono-SIO2 with durable stability at ordinary temp and its hybridized materaial |
| CN101497749A (en) * | 2009-03-06 | 2009-08-05 | 浙江池禾化工有限公司 | Surface modified nano silicon dioxide and acrylic resin coating containing the same |
| CN102604006A (en) * | 2012-03-09 | 2012-07-25 | 太原理工大学 | Preparation method for acidic silica sol in-situ modified acrylate emulsion |
Non-Patent Citations (3)
| Title |
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| 亲油性纳米二氧化硅的制备及其在聚酯涂料中的应用;李志虎;《中国优秀博硕士学位论文全文数据库工程科技Ⅰ辑》;20060815(第8期);6-7,17-18,21 * |
| 纳米二氧化硅/聚丙烯酸酯复合乳液的合成及其涂膜性能;张佼如等;《电镀与涂饰》;20120930;第31卷(第9期);59-65 * |
| 酯化改性纳米二氧化硅及其在聚酯漆中应用;张超灿等;《武汉理工大学学报》;20070531;第29卷(第5期);14-16 * |
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