CN104629494B - Polycarboxyl silicon dioxide nanoparticles and preparation method thereof - Google Patents
Polycarboxyl silicon dioxide nanoparticles and preparation method thereof Download PDFInfo
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- CN104629494B CN104629494B CN201510045983.5A CN201510045983A CN104629494B CN 104629494 B CN104629494 B CN 104629494B CN 201510045983 A CN201510045983 A CN 201510045983A CN 104629494 B CN104629494 B CN 104629494B
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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, more particularly to a kind of multi-carboxylation silica nanometer
Grain and preparation method thereof, belongs to composite and catalyst preparation field.
Background technology
Nano SiO 2 particle obtains extensively application in modern industry, draws in silica nanoparticle surface
Entering carboxyl can not only improve the interface compatibility of bead particle and matrix material etc., it is often more important that the broad reaction range of carboxyl
The very high reactivity of particle is imparted with the characteristic for being easy to ionize, makes it possible to be widely used in polymer modification
The field such as agent, water treatment agent, catalyst and carrier material, microcapsule embedded.
Show that the method for introducing carboxyl is much reported in hydroxy dioxetane SiClx nano particle, be mostly first with amino
Hydroxy dioxetane SiClx nano grain surface amination is recycled succinic anhydride, benzoyl oxide etc. and surface ammonia by silane coupler
Base reacts.Because silane coupler and hydroxy dioxetane silicon carbide particle will consume three silanol hydroxyls on surface when reacting(Si-OH),
Therefore, such method is often reacted three silanol hydroxyls and only introduces a carboxyl, carboxylic in hydroxy dioxetane SiClx nano grain surface
Base low degree.First carboxy-silane coupling agent is obtained by the reaction such as amino silicane coupling agent and succinic anhydride, maleic anhydride, is processed
Equally carboxyl can be introduced on hydroxy dioxetane silicon carbide particle surface during hydroxy dioxetane SiClx nano particle, but this method is not only equally existed
Carboxyl introduces the few shortcoming of relative quantity, and, carboxy-silane coupling agent is in the reaction condition with the presence of water due to self-crosslinking
A large amount of side reactions can be caused.
Directly by the acid anhydrides such as maleic anhydride and the silanol hydroxyl of hydroxy dioxetane SiClx nano grain surface(Si-OH)Reaction is drawn
The method for entering carboxyl is simple and feasible, but because carboxyl passes through silanol ester linkage on nano SiO 2 particle, silanol ester bond is easy
In hydrolysis and chemical bond is unstable.First hydroxy dioxetane SiClx nano particle is processed with mercaptosilane coupling agents, then with maleic
Dicarboxylic anhydride and silica nanoparticle surface sulfydryl addition, hydrolyze again discharge two carboxyls method reaction condition it is gentle
(Referring to document: Synthesis of mesoporous silica nanoparticale-oxaliplatin
conjugates for improved anticancer drug delivery. Colloid and surface B:
Biointerfaces,117,2014:75~81), and, silane coupler and three silicon of hydroxy dioxetane SiClx nano grain surface
Alcoholic extract hydroxyl group can introduce two carboxyls while reaction.
The method for once introducing multiple carboxyls in hydroxy dioxetane SiClx nano grain surface also has been reported that(Referring to 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 for adopting is with ammonia ethamine propyl trialkoxy
Silane coupler processes hydroxy dioxetane SiClx nano particle, hydroxy dioxetane SiClx nano grain surface be bonded simultaneously primary amino radical and
Secondary amino group, most three carboxyls can be introduced using primary amino radical and secondary amino group with chloroacetate reaction.But due to chlorine in processing procedure
Acetic acid has highly acid and acylation ability, can cause to generate the side reaction of chloroacetamide during the course of the reaction, and this has a strong impact on
Carboxylated degree.
The content of the invention
The present invention is directed to prior art when modified to hydroxy dioxetane SiClx nano grain surface carboxylated, existing carboxylic
Base introduction volume is few, the deficiency that modified product surface-bound carboxylic content is not high, and by two-step reaction a kind of how carboxy-modified dioxy is prepared
SiClx nano particle, realizes introducing three while hydroxy dioxetane SiClx nano grain surface often reacts three silanol hydroxyls of consumption
Individual or more than three carboxyls, obtain the modified silica nanoparticle of high-carboxyl-content.The modified dioxy of the multi-carboxylation of offer
SiClx nano particle also has preparation technology easy, and gently, raw material are easy to get reaction condition, are suitable for the spy of industrialized production
Point.
To achieve the above object of the invention, a kind of many carboxyl nano SiO 2 particles of offer are provided,
Its structural formula is as follows:
,
Wherein, R is 3,4,5- tri- carboxyl valeryls;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 includes a kind of preparation method of many carboxyl nano SiO 2 particles as above, step
It is rapid as follows:
1st, hydroxy dioxetane SiClx nano grain surface is processed
By weight, 1 part of hydroxy dioxetane SiClx nano particle is added in 3~200 parts of ketones solvents, suspension ultrasound
Ripple 1~60min of decentralized processing, adds 0.2~2 part of amino silicane coupling agent and is dissolved in the solution formed in ketones solvent;
The mixture for arriving back flow reaction at 40~90 DEG C after 1~8 hour, stops reaction, is cooled to room temperature, centrifugation, in temperature
For dried process under conditions of 80~100 DEG C 0.5~3 hour, amination nano SiO 2 particle is obtained;
2nd, carboxylated is processed
By weight, put into 1~5 part successively in the reactor and be dried ether solvent and 1~10 part of BTCA, in nitrogen
Under gas shielded, 0.5~3 part is added dropwiseN,N′- carbonyl dimidazoles be dissolved in 1~5 part be dried in ether solvent formed solution, 1~5
Hour completion of dropping, reacts 1~10 hour under room temperature condition, adds the amination nano SiO 2 particle that step 1 is obtained,
Continue to react 1~10 hour under room temperature condition, stop reaction, obtain reaction suspension;
3rd, the reaction suspension centrifugation for obtaining step 2, the nano SiO 2 particle for obtaining carboxylated process is consolidated
Body product;With distill water washing after be centrifuged again, repeated washing 2~6 times, by the product isolated temperature be 80~
Dried process under conditions of 100 DEG C, obtains multi-carboxylation nano SiO 2 particle.
When hydroxy dioxetane SiClx nano grain surface of the present invention is processed, ketones solvent is acetone, butanone or hexamethylene
Any one in ketone, or the wherein any two kinds mixed solvents mixed according to any mass ratio.Described hydroxy dioxetane SiClx
During nano grain surface process, Animoalkylsilane Coupling Agent is aminopropyl trimethoxysilane, aminopropyl triethoxysilane, ammonia
Any one in second aminopropyl trimethoxysilane and ammonia second aminopropyl triethoxysilane.Described carboxylated makes when processing
It is any one in tetrahydrofuran, ether or 1,4- dioxane with ether solvent.
The present invention mechanism be:With amino silicane coupling agent process hydroxy dioxetane SiClx nano particle, silane coupler with
Three silanol hydroxyl reactions on hydroxy dioxetane SiClx nano grain surface, are bonded to silane coupler hydroxy dioxetane SiClx and receive
Rice grain;Activated BTCA of carboxyl is subsequently adding, activated carboxyl is newly introduced with silica particles
Amino reaction, thus multiple carboxyls are introduced into aminosilica surface, how carboxy-modified nano SiO 2 particle is obtained.
The invention discloses a kind of how carboxy-modified nano SiO 2 particle and preparation method thereof, obtains surface carboxyl groups and contains
The high modified silica nanoparticle of amount.Compared with prior art, technical scheme its advantage of present invention offer is:
1st, the present invention is carboxylated raw material and amino dioxy using the BTCA containing multiple carboxyls in molecular structure
SiClx nano grain surface amino reacts, when polycarboxylic acid is bonded to nano SiO 2 particle by amide groups, BTCA
Remaining three carboxyls realize silica dioxide granule multi-carboxylation, many in the carboxyl number of silica surface introducing after process, carboxylic
Base content is high.
2nd, it is rear modification that carboxyl introduces process, and silica nanoparticle surface carboxyl-content is easy to regulation and control.
3rd, how carboxy-modified silica product prepares that reaction condition is gentle, preparation technology is easy, and raw material are easy to get, it is easy to
Industrialized production and popularization and application.
Description of the drawings
Fig. 1 is by how carboxy-modified nano SiO 2 particle provided in an embodiment of the present invention and unmodified hydroxy dioxetane
The INFRARED ABSORPTION correlation curve collection of illustrative plates of SiClx nano particle.
Fig. 2 is the SEM by how carboxy-modified nano SiO 2 particle provided in an embodiment of the present invention
Figure, wherein, modified silica nanoparticle particle diameter is about 230nm.
Specific embodiment
With reference to the accompanying drawings and examples the invention will be further described.
Embodiment 1
(1)The process of hydroxy dioxetane SiClx nano grain surface
100g tetrahydrofurans are added in 1000mL there-necked flasks(THF)With the hydroxy dioxetane that 10 g particle diameters are 300nm
Nano silicon particles(It is commercially available), suspension ultrasonic wave decentralized processing 10min adds 22.1 g 3- aminopropyl triethoxysilanes
(APTES)It is dissolved in the solution formed in 20g tetrahydrofurans.Mixture back flow reaction at 60 DEG C after 6 hours, stops reaction,
Room temperature is cooled to, centrifugation is dried 1 hour at 90 DEG C, obtains aminosilica nano particle.
(2)Carboxylated process
30 g tetrahydrofurans and 23.4 g BTCAs, nitrogen protection, drop are sequentially added in 500 mL there-necked flasks
Plus 16.2 gN,N'- carbonyl dimidazoles(CDI)The solution formed in 50 gTHF is dissolved in, time for adding was controlled at 1.5 hours.
The h of rear room temperature reaction 5 is added, above-mentioned aminopropyl nano SiO 2 particle is added, continues to react 6 hours, stop reaction.
(3)Post processing
The reaction suspension centrifugation for obtaining goes out modified silica nanoparticle, and solid product is washed with 10g distillations
Wash, washing terminates rear centrifugation and goes out modified silica nanoparticle.Repeated washing, centrifugation go out product, total coprocessing 4
It is secondary.Washing is dried to obtain product after terminating at 100 DEG C.
Product molecule structure is as follows:
,
Wherein, R is 3,4,5- tri- carboxyl valeryls;
y =1~100;w=1~100;The integer of x=5 ~ 100.
Embodiment 2
(1)The process of hydroxy dioxetane SiClx nano grain surface
150g tetrahydrofurans are added in 1000mL there-necked flasks(THF)It is 50nm hydroxylating titanium dioxides with 10 g particle diameters
Nano silicon particles, suspension ultrasonic wave decentralized processing 15min adds the dissolving of 26.5 g ammonia second aminopropyl triethoxysilanes
The solution formed in 20g tetrahydrofurans.Mixture back flow reaction at 65 DEG C after 5 hours, stops reaction, is cooled to room temperature,
Centrifugation, is dried 1 hour at 92 DEG C, obtains aminosilica nano particle.
(2)Carboxylated process
50 g tetrahydrofurans and 46.8 g BTCAs, nitrogen protection, drop are sequentially added in 500 mL there-necked flasks
Plus 32.4 gN,N'- carbonyl dimidazoles(CDI)The solution formed in 70 gTHF is dissolved in, time for adding was controlled at 2 hours.Plus
The complete h of rear room temperature reaction 5, adds above-mentioned ammonia second aminopropyl nano SiO 2 particle, continues to react 6 hours, stops reaction.
(3)Post processing
The reaction suspension centrifugation for obtaining goes out modified silica nanoparticle, and solid product is washed with 12g distillations
Wash, washing terminate after again centrifugation go out modified silica nanoparticle.Repeated washing, centrifugation go out product, altogether
Process 4 times.Washing is dried to obtain product after terminating at 100 DEG C.Product molecule structure is as follows:
,
Wherein, R is 3,4,5- tri- carboxyl valeryls;
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 is prepared is shown in accompanying drawing 1.
Referring to accompanying drawing 1, it is the how carboxy-modified nano SiO 2 particle and unmodified hydroxyl that the present embodiment is provided
The INFRARED ABSORPTION correlation curve collection of illustrative plates of nano SiO 2 particle.In modified silica nanoparticle infrared absorption curve,
FTIR: 3139.1 (-COOH), 2996.2 (CH2), 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) absworption peak.
Referring to accompanying drawing 2, it is the SEM of the how carboxy-modified nano SiO 2 particle that the present embodiment is provided
Figure, how carboxy-modified nano SiO 2 particle particle diameter is about 230nm.
Embodiment 3
(1)The process of hydroxy dioxetane SiClx nano grain surface
120g1,4- dioxane and 8 g particle diameters are added in 1000mL there-necked flasks for the hydroxylating titanium dioxide of 100nm
Nano silicon particles, suspension ultrasonic wave decentralized processing 15min adds the dissolving of 26.5 g ammonia second aminopropyl trimethoxysilanes
The solution formed in 25g1,4- dioxane.Mixture back flow reaction at 58 DEG C after 5 hours, stops reaction, is cooled to room
Temperature, centrifugation is dried 1 hour at 90 DEG C, obtains aminosilica nano particle.
(2)Carboxylated process
60 g1,4- dioxane and 46.8 g BTCAs are sequentially added in 500 mL there-necked flasks, nitrogen is protected
Shield, is added dropwise 31.9 gN,N'- carbonyl dimidazoles(CDI)65 g1 are dissolved in, the solution formed in 4- dioxane, time for adding
Control was at 1.5 hours.The h of rear room temperature reaction 5 is added, above-mentioned ammonia second aminopropyl nano SiO 2 particle is added, continues to react
7 hours, stop reaction.
(3)Post processing
The reaction suspension centrifugation for obtaining goes out modified silica nanoparticle, and solid product is washed with 10g distillations
Wash, washing terminate after again centrifugation go out modified silica nanoparticle.Repeated washing, centrifugation go out product, altogether
Process 6 times.Washing is dried to obtain product after terminating at 100 DEG C.Product molecule structure is as follows:
,
Wherein, R is 3,4,5- tri- carboxyl valeryls;
y =1~100;w=1~100;The integer of x=5 ~ 100.
Claims (5)
1. a kind of many carboxyl nano SiO 2 particles, it is characterised in that its structural formula is as follows:
,
Wherein, R is 3,4,5- tri- carboxyl valeryls;M=2 or 3;N=0 or 1;
Y=1~100;W=1~100;The integer of x=5~100.
2. a kind of preparation method of many carboxyl nano SiO 2 particles as claimed in claim 1, it is characterised in that include as
Lower step:
(1) hydroxy dioxetane SiClx nano grain surface is processed
By weight, 1 part of hydroxy dioxetane SiClx nano particle is added in 3~200 parts of ketones solvents, suspension ultrasound wavelength-division
Dissipate and process 1~60min, add and the solution formed in ketones solvent is dissolved in by 0.2~2 part of amino silicane coupling agent;Obtain
Mixture at 40~90 DEG C back flow reaction after 1~8 hour, stop reaction, be cooled to room temperature, centrifugation is in temperature
Dried process 0.5~3 hour under conditions of 80~100 DEG C, obtains amination nano SiO 2 particle;
(2) carboxylated is processed
By weight, put into 1~5 part successively in the reactor and be dried ether solvent and 1~10 part of BTCA, protect in nitrogen
Under shield, it is added dropwise by 0.5~3 partN,N′- carbonyl dimidazoles are dissolved in 1~5 part and are dried the solution formed in ether solvent, and 1~5 is little
When completion of dropping, under room temperature condition react 1~10 hour, add step(1)The amination nano SiO 2 particle for obtaining,
Continue to react 1~10 hour under room temperature condition, stop reaction, obtain reaction suspension;
(3) by step(2)The reaction suspension centrifugation for obtaining, obtains the nano SiO 2 particle solid of carboxylated process
Product;With distill water washing after be centrifuged again, repeated washing 2~6 times, by the product isolated temperature be 80~
Dried process under conditions of 100 DEG C, obtains multi-carboxylation nano SiO 2 particle.
3. the preparation method of multi-carboxylation nano SiO 2 particle according to claim 2, it is characterised in that:Described
During the process of hydroxy dioxetane SiClx nano grain surface, ketones solvent is any one in acetone, butanone or cyclohexanone, or wherein
Any two kinds 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 characterised in that:Described
During the process of hydroxy dioxetane SiClx nano grain surface, amino silicane coupling agent is aminopropyl trimethoxysilane, the second of aminopropyl three
Any one in TMOS, ammonia second aminopropyl trimethoxysilane and ammonia second aminopropyl triethoxysilane.
5. the preparation method of multi-carboxylation nano SiO 2 particle according to claim 2, it is characterised in that:Described
Carboxylated process when using ether solvent be tetrahydrofuran, ether or 1,4- dioxane in any one.
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Effective date of registration: 20190409 Address after: 215228 North Ring Road, Shengze Town, Wujiang District, Suzhou City, Jiangsu Province, 1988 Patentee after: Jiangsu Hua Hao silk Limited by Share Ltd Address before: 215123 199 Ren Yan Road, Suzhou Industrial Park, Suzhou, Jiangsu Patentee before: Soochow University |