CN104629494A - Polycarboxyl silicon dioxide nanoparticles and preparation method thereof - Google Patents
Polycarboxyl silicon dioxide nanoparticles and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polycarboxyl silicon dioxide nanoparticles and a preparation method thereof. The preparation method comprises the following steps: by using hydroxy silicon dioxide nanoparticles as the initial raw material, treating with an aminosilane coupling agent to introduce reactive amino or amine group, and reacting with N,N-carbonyldiimidazole-activated butane tetrabasic carboxylic acid under very mild conditions to introduce 3,4,5-tricarboxylvaleryl group onto the surface of the hydroxy silicon dioxide nanoparticles, thereby obtaining the surface-polycarboxylated modified silicon dioxide nanoparticles. By using the butane tetrabasic carboxylic acid to perform carboxylation modification on the hydroxy silicon dioxide nanospheres, the polycarboxyl silicon dioxide nanoparticles have the advantages of high carboxyl content and controllable carboxyl content; and since the reaction conditions for the N,N-carbonyldiimidazole-activated butane tetrabasic carboxylic acid and amino group are very mild, the reaction is easy to perform and is complete. The method disclosed by the invention has the advantages of simple preparation technique and accessible raw materials, and is easy for industrial production and popularization.
Description
Technical field
The present invention relates to a kind of carboxyl nano SiO 2 particle, particularly a kind of multi-carboxylation nano SiO 2 particle and preparation method thereof, belong to matrix material and catalyst preparation field.
Background technology
Nano SiO 2 particle obtains widespread use in modern industry, the interface compatibility that carboxyl not only can improve bead particle and body material etc. is introduced at silica nanoparticle surface, the more important thing is the reaction range of carboxyl broadness and be easy to Ionized characteristic and impart the very high reactive behavior of particle, making it to be widely used in polymer modification agent, water conditioner, catalyzer and solid support material, the field such as microcapsule embedded.
Show to introduce the existing a lot of report of method of carboxyl at hydroxy dioxetane SiClx nano particle, be mostly first utilize amino silicane coupling agent by the amination of hydroxy dioxetane SiClx nano grain surface, recycling Succinic anhydried, benzoyl oxide etc. react with surface amino groups.Due to three silanol hydroxyls (Si-OH) on the surface will be consumed when silane coupling agent and hydroxy dioxetane silicon carbide particle react, therefore, such method is often reacted three silanol hydroxyls at hydroxy dioxetane SiClx nano grain surface and is only introduced a carboxyl, and carboxylated degree is low.First react obtained carboxy-silane coupling agent by amino silicane coupling agent and Succinic anhydried, maleic anhydride etc., carboxyl can be introduced on hydroxy dioxetane silicon carbide particle surface equally during process hydroxy dioxetane SiClx nano particle, but this method not only exists carboxyl equally introduces the few shortcoming of relative quantity, and, carboxy-silane coupling agent in the reaction conditions having water to exist because self-crosslinking can cause a large amount of side reaction.
Directly react by the silanol hydroxyl (Si-OH) of the acid anhydrides such as maleic anhydride and hydroxy dioxetane SiClx nano grain surface the method introducing carboxyl simple and feasible, but because carboxyl passes through silanol ester linkage on nano SiO 2 particle, silanol ester bond is easy to hydrolysis and chemical bond is unstable.First with mercaptosilane coupling agents process hydroxy dioxetane SiClx nano particle, then with MALEIC ANHYDRIDE and the addition of silica nanoparticle surface sulfydryl, hydrolysis discharges the method reaction conditions gentleness of two carboxyls (see document: Synthesis of mesoporous silica nanoparticale-oxaliplatin conjugates for improved anticancer drug delivery. Colloid and surface B:Biointerfaces again, 117, 2014:75 ~ 81), and, two carboxyls can be introduced while silane coupling agent and hydroxy dioxetane SiClx nano grain surface three silanol hydroxyl reactions.
The method once introducing multiple carboxyl at hydroxy dioxetane SiClx nano grain surface also has report (see document: Prepration and characterization of multi-carbonyl-functionalized silica gel for removal of Cu (II), Cd (II), Ni (II) and Zn (II) from aqueous solution. Applied surface Science, 314, 2014:1063 ~ 1069), the scheme adopted is with ammonia ethamine propyl trialkoxy silane coupling agent treatment hydroxy dioxetane SiClx nano particle, at hydroxy dioxetane SiClx nano grain surface bonding primary amino and secondary amino group simultaneously, utilize primary amino and secondary amino group and chloroacetate reaction can introduce maximum three carboxyls.But because Mono Chloro Acetic Acid in treating processes has strongly-acid and acylations ability, can cause the side reaction generating chlor(o)acetamide in reaction process, this has had a strong impact on carboxylated degree.
Summary of the invention
The present invention is directed to prior art when modification carboxylated to hydroxy dioxetane SiClx nano grain surface, the existing deficiency that carboxyl introduction volume is few, modified product surface-bound carboxylic content is not high, the how carboxy-modified nano SiO 2 particle of one is prepared by two-step reaction, realize introducing more than three or three carboxyls while hydroxy dioxetane SiClx nano grain surface often reacts consumption three silanol hydroxyls, obtain the modified silica nanoparticle of high-carboxyl-content.It is easy that the multi-carboxylation modified silica nanoparticle provided also has preparation technology, and reaction conditions is gentle, and starting material are easy to get, and are suitable for the feature of suitability for industrialized production.
To achieve the above object of the invention, technical scheme of the present invention is to provide a kind of many carboxyls nano SiO 2 particle, and its structural formula is as follows:
,
Wherein, R is 3,4,5-tri-carboxyl pentanoyl
;m=2 or 3; N=0 or 1;
Y=1 ~ 100; W=1 ~ 100; The integer of x=5 ~ 100.
Technical solution of the present invention also comprises a kind of preparation method of many carboxyls nano SiO 2 particle as above, and step is as follows:
1, hydroxy dioxetane SiClx nano grain surface process
By weight, 1 part of hydroxy dioxetane SiClx nano particle is joined in 3 ~ 200 parts of ketones solvents, suspension ultrasonic wave dispersion treatment 1 ~ 60min, then add 0.2 ~ 2 part of amino silicane coupling agent and be dissolved in the solution formed in ketones solvent; Back flow reaction is after 1 ~ 8 hour at 40 ~ 90 DEG C for the mixture obtained, and stopped reaction, is cooled to room temperature, centrifugation, is drying treatment 0.5 ~ 3 hour under the condition of 80 ~ 100 DEG C, obtains amination nano SiO 2 particle in temperature;
2, carboxylated process
By weight, drop into 1 ~ 5 part of dry ether solvent and 1 ~ 10 part of BTCA in the reactor successively, under nitrogen protection, drip 0.5 ~ 3 part
n, N '-carbonyl dimidazoles is dissolved in the solution formed in 1 ~ 5 part of dry ether solvent, within 1 ~ 5 hour, dropwise, react 1 ~ 10 hour under room temperature condition, add the amination nano SiO 2 particle that step 1 obtains again, reaction is continued 1 ~ 10 hour under room temperature condition, stopped reaction, obtains reaction suspension;
3, reaction suspension centrifugation step 2 obtained, obtains the nano SiO 2 particle solid product of carboxylated process; To carry out centrifugation again after distilled water wash, repeated washing 2 ~ 6 times, is drying treatment under the condition of 80 ~ 100 DEG C in temperature by isolated product, obtains multi-carboxylation nano SiO 2 particle.
During hydroxy dioxetane SiClx nano grain surface process of the present invention, ketones solvent is any one in acetone, butanone or pimelinketone, or wherein any two kinds of mixed solvents mixed according to any mass ratio.During described hydroxy dioxetane SiClx nano grain surface process, Animoalkylsilane Coupling Agent is any one in aminopropyl trimethoxysilane, aminopropyl triethoxysilane, ammonia second aminopropyl trimethoxysilane and ammonia second aminopropyl triethoxysilane.Use during described carboxylated process that ether solvent is tetrahydrofuran (THF), any one in ether or Isosorbide-5-Nitrae-dioxane.
Mechanism of the present invention is: with amino silicane coupling agent process hydroxy dioxetane SiClx nano particle, and three silanol hydroxyl reactions on silane coupling agent and hydroxy dioxetane SiClx nano grain surface, are bonded to hydroxy dioxetane SiClx nano particle by silane coupling agent; Then add the BTCA that a carboxyl is activated, the amino that activated carboxyl and silica particles are newly introduced reacts, and thus multiple carboxyl is introduced aminosilica surface, obtained how carboxy-modified nano SiO 2 particle.
The invention discloses how carboxy-modified nano SiO 2 particle of one and preparation method thereof, obtain the modified silica nanoparticle that surface-bound carboxylic content is high.Compared with prior art, its beneficial effect of technical scheme provided by the invention is:
1, the present invention utilizes the BTCA containing multiple carboxyl in molecular structure to be that carboxylated raw material and aminosilica nano grain surface amino react, when poly carboxylic acid is bonded to nano SiO 2 particle by amide group, BTCA remains three carboxyls and realizes silica dioxide granule multi-carboxylation, many at the carboxyl number of silica sphere introducing after process, carboxyl-content is high.
2, carboxyl introduces process is rear modification, and silica nanoparticle surface carboxyl-content is easy to regulation and control.
3, how carboxy-modified silica product preparation feedback mild condition, preparation technology be easy, and starting material are easy to get, and is easy to suitability for industrialized production and applies.
Accompanying drawing explanation
Fig. 1 is the infrared absorption correlation curve collection of illustrative plates of how carboxy-modified nano SiO 2 particle and the unmodified hydroxy dioxetane SiClx nano particle provided by the embodiment of the present invention.
Fig. 2 is the scanning electron microscope diagram of the how carboxy-modified nano SiO 2 particle provided by the embodiment of the present invention, and wherein, modified silica nanoparticle particle diameter is about 230nm.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1
(1) hydroxy dioxetane SiClx nano grain surface process
The hydroxy dioxetane SiClx nano particle (commercially available) that 100g tetrahydrofuran (THF) (THF) and 10 g particle diameters are 300nm is added in 1000mL there-necked flask, suspension ultrasonic wave dispersion treatment 10min, then add 22.1 g 3-aminopropyl triethoxysilanes (APTES) and be dissolved in the solution formed in 20g tetrahydrofuran (THF).Back flow reaction is after 6 hours at 60 DEG C for mixture, and stopped reaction, is cooled to room temperature, centrifugation, and at 90 DEG C, drying 1 hour, obtains aminosilica nano particle.
(2) carboxylated process
In 500 mL there-necked flasks, add 30 g tetrahydrofuran (THF)s and 23.4 g BTCA successively, nitrogen protection, drips 16.2 g
n, N'-carbonyl dimidazoles (CDI) is dissolved in the solution formed in 50 gTHF, and time for adding controlled at 1.5 hours.Add rear room temperature reaction 5 h, then add above-mentioned aminopropyl nano SiO 2 particle, continue reaction 6 hours, stopped reaction.
(3) aftertreatment
The reaction suspension centrifugation obtained goes out modified silica nanoparticle, and solid product is with 10g distilled water wash, and washing terminates rear centrifugation and goes out modified silica nanoparticle.Repeated washing, centrifugation go out product, total co-processing 4 times.After washing terminates, at 100 DEG C, drying obtains product.
Product molecule structure is as follows:
,
Wherein, R is 3,4,5-tri-carboxyl pentanoyl
;
Y=1 ~ 100; W=1 ~ 100; The integer of x=5 ~ 100.
Embodiment 2
(1) hydroxy dioxetane SiClx nano grain surface process
150g tetrahydrofuran (THF) (THF) is added and 10 g particle diameters are 50nm hydroxylation nano SiO 2 particle in 1000mL there-necked flask, suspension ultrasonic wave dispersion treatment 15min, then add 26.5 g ammonia second aminopropyl triethoxysilanes and be dissolved in the solution formed in 20g tetrahydrofuran (THF).Back flow reaction is after 5 hours at 65 DEG C for mixture, and stopped reaction, is cooled to room temperature, centrifugation, and at 92 DEG C, drying 1 hour, obtains aminosilica nano particle.
(2) carboxylated process
In 500 mL there-necked flasks, add 50 g tetrahydrofuran (THF)s and 46.8 g BTCA successively, nitrogen protection, drips 32.4 g
n, N'-carbonyl dimidazoles (CDI) is dissolved in the solution formed in 70 gTHF, and time for adding controlled at 2 hours.Add rear room temperature reaction 5 h, then add above-mentioned ammonia second aminopropyl nano SiO 2 particle, continue reaction 6 hours, stopped reaction.
(3) aftertreatment
The reaction suspension centrifugation obtained goes out modified silica nanoparticle, and solid product is with 12g distilled water wash, and washing terminates rear recentrifuge and isolates modified silica nanoparticle.Repeated washing, centrifugation go out product, total co-processing 4 times.After washing terminates, at 100 DEG C, drying obtains product.Product molecule structure is as follows:
,
Wherein, R is 3,4,5-tri-carboxyl pentanoyl
;
Y=1 ~ 100; W=1 ~ 100; The integer of x=5 ~ 100.
The infrared absorption curve of the multi-carboxylation nano SiO 2 particle that the present embodiment prepares is shown in accompanying drawing 1.
See accompanying drawing 1, it is the infrared absorption correlation curve collection of illustrative plates of the how carboxy-modified nano SiO 2 particle that provides of the present embodiment and unmodified hydroxy dioxetane SiClx nano particle.In modified silica nanoparticle infrared absorption curve, FTIR:3139.1 (-COOH), 2996.2 (CH
2), 1728.0 (C=O, carboxyls), 1477.8 (C-Si), 1265.5,1094.1 (Si-O) cm
-1.3139.1 cm are had no in the infrared absorption curve of unmodified hydroxy dioxetane SiClx nano particle
-1(-COOH) and 1728.0 cm
-1(C=O, carboxyl) absorption peak.
See accompanying drawing 2, it is the scanning electron microscope diagram of the how carboxy-modified nano SiO 2 particle that the present embodiment provides, and how carboxy-modified nano SiO 2 particle particle diameter is about 230nm.
Embodiment 3
(1) hydroxy dioxetane SiClx nano grain surface process
120g1 is added in 1000mL there-necked flask, 4-dioxane and 8 g particle diameters are the hydroxylation nano SiO 2 particle of 100nm, suspension ultrasonic wave dispersion treatment 15min, then add 26.5 g ammonia second aminopropyl trimethoxysilane and be dissolved in 25g1, the solution formed in 4-dioxane.Back flow reaction is after 5 hours at 58 DEG C for mixture, and stopped reaction, is cooled to room temperature, centrifugation, and at 90 DEG C, drying 1 hour, obtains aminosilica nano particle.
(2) carboxylated process
In 500 mL there-necked flasks, add 60 g1 successively, 4-dioxane and 46.8 g BTCA, nitrogen protection, drips 31.9 g
n, N'-carbonyl dimidazoles (CDI) is dissolved in 65 g1, the solution formed in 4-dioxane, and time for adding controlled at 1.5 hours.Add rear room temperature reaction 5 h, then add above-mentioned ammonia second aminopropyl nano SiO 2 particle, continue reaction 7 hours, stopped reaction.
(3) aftertreatment
The reaction suspension centrifugation obtained goes out modified silica nanoparticle, and solid product is with 10g distilled water wash, and washing terminates rear recentrifuge and isolates modified silica nanoparticle.Repeated washing, centrifugation go out product, total co-processing 6 times.After washing terminates, at 100 DEG C, drying obtains product.Product molecule structure is as follows:
,
Wherein, R is 3,4,5-tri-carboxyl pentanoyl
;
Y=1 ~ 100; W=1 ~ 100; The integer of x=5 ~ 100.
Claims (5)
1. the nano SiO 2 particle of carboxyl more than, is characterized in that its structural formula is as follows:
,
Wherein, R is 3,4,5-tri-carboxyl pentanoyl
;m=2 or 3; N=0 or 1;
Y=1 ~ 100; W=1 ~ 100; The integer of x=5 ~ 100.
2. a preparation method for many carboxyls nano SiO 2 particle as claimed in claim 1, is characterized in that comprising the steps:
(1) hydroxy dioxetane SiClx nano grain surface process
By weight, 1 part of hydroxy dioxetane SiClx nano particle is joined in 3 ~ 200 parts of ketones solvents, suspension ultrasonic wave dispersion treatment 1 ~ 60min, then add 0.2 ~ 2 part of amino silicane coupling agent and be dissolved in the solution formed in ketones solvent; Back flow reaction is after 1 ~ 8 hour at 40 ~ 90 DEG C for the mixture obtained, and stopped reaction, is cooled to room temperature, centrifugation, is drying treatment 0.5 ~ 3 hour under the condition of 80 ~ 100 DEG C, obtains amination nano SiO 2 particle in temperature;
(2) carboxylated process
By weight, drop into 1 ~ 5 part of dry ether solvent and 1 ~ 10 part of BTCA in the reactor successively, under nitrogen protection, drip 0.5 ~ 3 part
n, N '-carbonyl dimidazoles is dissolved in the solution formed in 1 ~ 5 part of dry ether solvent, within 1 ~ 5 hour, dropwise, react 1 ~ 10 hour under room temperature condition, add the amination nano SiO 2 particle that step (1) obtains again, reaction is continued 1 ~ 10 hour under room temperature condition, stopped reaction, obtains reaction suspension;
(3) by the reaction suspension centrifugation that step (2) obtains, the nano SiO 2 particle solid product of carboxylated process is obtained; To carry out centrifugation again after distilled water wash, repeated washing 2 ~ 6 times, is drying treatment under the condition of 80 ~ 100 DEG C in temperature by isolated product, obtains multi-carboxylation nano SiO 2 particle.
3. the preparation method of multi-carboxylation nano SiO 2 particle according to claim 2, it is characterized in that: during described hydroxy dioxetane SiClx nano grain surface process, ketones solvent is any one in acetone, butanone or pimelinketone, or wherein any two kinds of mixed solvents mixed according to any mass ratio.
4. the preparation method of multi-carboxylation nano SiO 2 particle according to claim 2, it is characterized in that: during described hydroxy dioxetane SiClx nano grain surface process, Animoalkylsilane Coupling Agent is any one in aminopropyl trimethoxysilane, aminopropyl triethoxysilane, ammonia second aminopropyl trimethoxysilane and ammonia second aminopropyl triethoxysilane.
5. the preparation method of multi-carboxylation nano SiO 2 particle according to claim 2, is characterized in that: use during described carboxylated process that ether solvent is tetrahydrofuran (THF), any one in ether or Isosorbide-5-Nitrae-dioxane.
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