CN101941705B - Method for preparing mesoporous silica from temperature-sensitive polymer structure directing agent - Google Patents
Method for preparing mesoporous silica from temperature-sensitive polymer structure directing agent Download PDFInfo
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Abstract
The invention discloses a method for preparing mesoporous silica from a temperature-sensitive polymer structure directing agent. The mesoporous silica is prepared by blending poly(N-isopropylamide) with temperature sensitivity or poly(N-isopropylamide)-based hydrophilic copolymer aqueous solution and sodium silicate pre-hydrolyzing solution, hydrolyzing the mixture for 1 hour at the room temperature, washing the reactant with water of which the temperature is less than 30 DEG C and drying the reactant. The principle of the invention is that a mesoporous structure is adjusted and the structure directing agent is removed by taking advantage of the temperature sensitivity of the poly(N-isopropylamide), namely the characteristic that the poly(N-isopropylamide) is dissolved in water at the temperature of below the lower critical solution temperature (LCST) and is formed into mesoscopic microspheres at the temperature of above the LCST. By the method, the structure directing agent is removed without high-temperature calcination and organic solvent extraction; and the mesoporous structure of silica is adjusted in multiple ways, such as changing the ageing temperature, the ratio of the structure directing agent to a silica source and the structure of the structure directing agent and the like. The method is an environment-friendly preparation method with low cost.
Description
Affiliated technical field
The present invention relates to the preparation method in a kind of inorganic mesoporous material technology field, specifically prepare the method for mesoporous silicon oxide with the temperature sensing polymer structure directing agent.
Background technology
Inorganic mesoporous material has big specific surface area, adjustable meso-hole structure and can all be with a wide range of applications in every field such as catalysis, absorption, separation by the character of finishing.The preparation method commonly used of existing mesoporous silicon material generally is to use ionogenic surfactant such as cetyl trimethylammonium bromide (CTAB) or neutral surface active agent such as T 46155-b-polyoxypropylene-b-T 46155 (PEO-b-PPO-b-PEO) as structure directing agent.These ionogenic surfactants and neutral-surface are lived agent as structure directing agent, and they possess significant advantage, and promptly mesoporous silicon material aperture homogeneous, the pore structure of preparation are regular.But; Use ionogenic surfactant or neutral surface active agent to prepare mesoporous silicon oxide as structure directing agent; Generally need just can remove structure directing agent with the method for high-temperature calcination or organic solvent extraction, this can increase preparation cost on the one hand, also can cause environmental pollution; On the other hand, in the incinerating process, also can cause mesoporous caving in, destroy the structure of mesoporous silicon oxide.In recent years; Reported that a lot of use nonsurfactant structure directing agents prepare the novel method of mesoporous silicon oxide, do not used ionogenic surfactant or neutral surface active agent to prepare the problem that exists in the method for mesoporous silicon oxide as structure directing agent but thoroughly change.Document Adv.Mater.3; 313-316 (1998) has reported a kind of by nonsurfactant; Like L-dibenzoyl tartaric acid, D-glucose and D-SANMALT-S; Prepare the method for mesoporous silicon oxide as structure directing agent, but that this method uses expensive tetraethoxy TEOS to do silicon source, reaction and treatment time is long.Document Chem.Mater.12; 1513-1515 (2000) has reported a kind of method that is prepared mesoporous silicon oxide by dendritic macromole as structure directing agent; But the same expensive tetraethoxy TEOS of use of this method does the silicon source, dendritic macromole is difficult for preparing and productive rate is low; And this method uses 550 ℃ of calcining method to remove structure directing agent, not only causes environmental pollution but also cost higher.
Summary of the invention
The present invention will have the homopolymer that gathers (N-NSC 11448) of temperature sensitive property or based on the hydrophilic copolymers that gathers (N-NSC 11448) as structure directing agent, prepare mesoporous silicon oxide with cheap water glass as the silicon source.Simple, low, the environmental protection of cost of this method preparation has solved existing use nonsurfactant and has prepared the problem that exists in the mesoporous silicon material as structure directing agent.This method has three characteristics: the meso-hole structure of mesoporous silicon oxide can be regulated through changing aging temperature in (1); Promptly when aging temperature from gathering (N-NSC 11448) or being elevated to LCST below the lowest critical solution temperature (LCST) based on the hydrophilic copolymers that gathers (N-NSC 11448) when above; Gather (N-NSC 11448) or change spheroidal aggravation based on the hydrophilic copolymers structure directing agent that gathers (N-NSC 11448) into from hydrophilic segment, the hole dimension of mesoporous silicon oxide increases; (2) can gather (N-NSC 11448) or regulate the meso-hole structure of mesoporous silicon oxide based on the molecular weight of the hydrophilic copolymers that gathers (N-NSC 11448) through change.Gather (N-NSC 11448) or can be through several different methods preparations such as radical polymerization, atom transferred free radical living polymerization and reversible addition fracture polymerizations based on the hydrophilic copolymers that gathers (N-NSC 11448); Through changing homopolymer or the multipolymer that polymerizing condition can obtain different molecular weight easily, the variety of polymer architecture directed agents provides possibility for the meso-hole structure of regulating mesoporous silicon oxide; (3) can the structure directing agent in the silicon-dioxide be removed through way with water washing.Low below the critical solution temperature LCST; The gathering (N-NSC 11448) or be water miscible of temperature sensitive property based on the hydrophilic copolymers that gathers (N-NSC 11448); Can remove structure directing agent with the way of water washing, avoid the caused problem of high-temperature calcination and organic solvent extraction.
The purpose of this invention is to provide that a kind of cost is low, preparation is simple, environmental protection, the novel method for preparing mesoporous silicon oxide with temperature sensing polymer as structure directing agent.
A kind ofly prepare the method for mesoporous silicon oxide with the temperature sensing polymer structure directing agent, comprise the steps: one, through radical polymerization, atom transferred free radical living polymerization and reversible addition fracture polymeric polymerization method synthetic have temperature sensitive property gather (N-NSC 11448) and based on the structure directing agent of the hydrophilic copolymers that gathers (N-NSC 11448) as the preparation mesoporous silicon oxide; Two, the pH value with certain density sodium silicate aqueous solution is adjusted to slightly acidic; Under room temperature and agitation condition; The acidifying sodium silicate aqueous solution is joined in the homopolymer and the aqueous solution based on the hydrophilic copolymers that gathers (N-NSC 11448) that gathers (N-NSC 11448); Obtain white depositions immediately, continue to stir 1 hour; Three, with reactant transfer in hydrothermal reaction kettle, left standstill at a certain temperature aging 24 hours; Four, reactant is naturally cooled to room temperature; Filter, collect white depositions, the water logging bubble of white depositions with 0～30 ℃ washed 2～3 times; Again once, at last the white precipitate of collecting vacuum-drying under 30 ℃ condition was promptly obtained mesoporous silicon oxide in 24 hours with washing with alcohol.
Among the present invention as the gathering of structure directing agent (N-NSC 11448) and based on the molecular weight Mw of the hydrophilic copolymers that gathers (N-NSC 11448) at 3000-300000g/mol, molecular weight dispersion coefficient PDI is between 1.05-5.00.
Comprise as the hydrophilic copolymers based on gathering (N-NSC 11448) of structure directing agent among the present invention and gather (N-NSC 11448-co-vinylformic acid), gather (N-NSC 11448-co-methylacrylic acid), gather (N-NSC 11448-co-acrylic amide), gather (N-NSC 11448-co-pyrrolidone) and gather (N-NSC 11448-co-vinyl alcohol).
Employed gathering in the step 2 (N-NSC 11448) and be 1～15g/l based on the concentration of the hydrophilic copolymers structure directing agent that gathers (N-NSC 11448).
The concentration of used sodium silicate aqueous solution is 1～15g/l in the step 2.
Regulate the used acid of sodium silicate aqueous solution pH in the step 2 and can be hydrochloric acid, sulfuric acid, perchloric acid, Hydrogen bromide or nitric acid.
The pH value of used sodium silicate solution is 4.0～7.0 in the step 2.
The required structure directing agent and the mass ratio of silicon-dioxide can be 1: 5～5: 1 in the step 2.
Needed aging temperature is 25～150 ℃ in the step 3.
Description of drawings
Fig. 1: the present invention prepares the principle schematic of mesoporous silicon oxide method.
Fig. 2: the mesoporous silicon oxide optical photograph of preparation in the instance 12.
Fig. 3: the mesoporous silicon oxide optical photograph of preparation in the instance 14.
Fig. 4: the mesoporous silicon oxide SEM photo of preparation in the instance 12.
Fig. 5: the mesoporous silicon oxide SEM photo of preparation in the instance 14.
Fig. 6: the mesoporous silicon oxide TEM photo of preparation in the instance 12.
Fig. 7: the mesoporous silicon oxide TEM photo of preparation in the instance 14.
Fig. 8: the N of the mesoporous silicon oxide of preparation in the instance 12
2The adsorption/desorption graphic representation.
Fig. 9: the N of the mesoporous silicon oxide of preparation in the instance 14
2The adsorption/desorption graphic representation.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Instance 1: N-NSC 11448 and the 0.14g Diisopropyl azodicarboxylate of 10.0g are joined in the glass reaction bottle, add 50ml ethanol again.At first, usefulness vacuumizes constantly stirring down/and the method for inflated with nitrogen removes the mixture dissolved oxygen, then 75 ℃ of polymerizations 5 hours.After polyreaction finishes, in reactant impouring 100ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 9.7g and gather (N-NSC 11448) (PNIPAM-1), yield is 97%, molecular weight Mw=1.82 * 10 of PNIPAM-1
4G/mol, molecular weight dispersion coefficient PDI=1.82.The correlation parameter of PNIPAM-1 is seen table 1.
Instance 2: N-NSC 11448 and the 0.35g Diisopropyl azodicarboxylate of 12.0g are joined in the glass reaction bottle, add 60ml ethanol again.At first, usefulness vacuumizes constantly stirring down/and the method for inflated with nitrogen removes the mixture dissolved oxygen, then 75 ℃ of polymerizations 6 hours.After polyreaction finishes, in reactant impouring 120ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 11.8g and gather (N-NSC 11448) (PNIPAM-2), yield is 98%, molecular weight Mw=3.1 * 10 of PNIPAM-2
4G/mol, molecular weight dispersion coefficient PDI=1.98.The correlation parameter of PNIPAM-2 is seen table 1.
Instance 3: N-NSC 11448 and the 0.29g Diisopropyl azodicarboxylate of 10.0g are joined in the glass reaction bottle, add 20ml ethanol again.At first, usefulness vacuumizes constantly stirring down/and the method for inflated with nitrogen removes the mixture dissolved oxygen, then 75 ℃ of polymerizations 5 hours.After polyreaction finishes, in reactant impouring 40ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 9.8g and gather (N-NSC 11448) (PNIPAM-3), yield is 98%, molecular weight Mw=5.15 * 10 of PNIPAM-3
4G/mol, molecular weight dispersion coefficient PDI=1.56.The correlation parameter of PNIPAM-3 is seen table 1.
Instance 4: N-NSC 11448 and the 0.72g Diisopropyl azodicarboxylate of 10.0g are joined in the glass reaction bottle, add 20ml ethanol again.At first, usefulness vacuumizes constantly stirring down/and the method for inflated with nitrogen removes the mixture dissolved oxygen, then 75 ℃ of polymerizations 5 hours.After polyreaction finishes, in reactant impouring 40ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 9.7g and gather (N-NSC 11448) (PNIPAM-4), yield is 97%, molecular weight Mw=9.32 * 10 of PNIPAM-4
4G/mol, molecular weight dispersion coefficient PDI=1.73.The correlation parameter of PNIPAM-4 is seen table 1.
Instance 5: with 0.20g cuprous chloride and 0.46g three (2-dimethylaminoethyl) amine (CAS number: 33527-91-2) join in the glass reaction bottle; Add 5.0ml toluene again; Then the N-NSC 11448 of 5.0g and the 2-methyl chloropropionate of 0.08g are added in the glass reaction bottle; And carry out freezing/vacuumize/thaw to remove dissolved oxygen, 40 ℃ of following polymerizations 24 hours.After polymerization is accomplished, add 10ml toluene earlier, pour reactant into the neutral alumina post then, collect effluent.Effluent is added dropwise in the 40ml ice ether, obtains white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 4.9g and gather (N-NSC 11448) (PNIPAM-5), yield is 98%, molecular weight Mw=9.3 * 10 of PNIPAM-5
3G/mol, molecular weight dispersion coefficient PDI=1.12.The correlation parameter of PNIPAM-5 is seen table 1.
Instance 6: N-NSC 11448,0.32g dithio benzyl benzoate and the 0.07g Diisopropyl azodicarboxylate of 10.0g are joined in the tubular type Glass Containers, add the N of 20ml again, dinethylformamide.Earlier with vacuumize/method of inflated with nitrogen removes dissolved oxygen, then the tubular type Glass Containers sealed.Place 65 ℃ oil bath or water-bath to react 36 hours the tubular type Glass Containers.After reaction finishes, earlier the 40ml THF is joined the tubular type Glass Containers, with in the reactant impouring 100ml ice ether, obtain pink throw out then.Filter and collect pink throw out, with pink throw out vacuum-drying at room temperature 1 day, obtain 9.8g and gather (N-NSC 11448) (PNIPAM-6), yield is 98%, molecular weight Mw=6.5 * 10 of PNIPAM-6
3G/mol, molecular weight dispersion coefficient PDI=1.14.The correlation parameter of PNIPAM-6 is seen table 1.
Instance 7: with PNIPAM-6 and the 100ml ethanol adding glass flask of 2.0g, feed nitrogen and remove the dissolved oxygen in the solution, add the 80% hydrazine aqueous solution of 1.0ml again, at room temperature reacted 1 hour by preparation in the instance 6.After reaction finishes, add the 0.1mol/l hydrochloric acid soln of 1ml, again solvent evaporation is obtained yellow powder.The yellow powder of collecting is dissolved in the 10ml THF, filters, collect filtrating.The filtrating of collecting is joined in the 40ml ice ether, faint yellow deposition occurs.Filter and collect faint yellow deposition, with the 80 ℃ hot washes of faint yellow deposition with 5ml, drying obtains 1.9g and gathers (N-NSC 11448) (PNIPAM-7), and yield is 95%, molecular weight Mw=6.5 * 10 of PNIPAM-7
3G/mol, molecular weight dispersion coefficient PDI=1.14.The correlation parameter of PNIPAM-7 is seen table 1.
Instance 8: N-NSC 11448,1.20g vinylformic acid and the 0.24g Diisopropyl azodicarboxylate of 4.80g are joined in the glass reaction bottle, add 70ml ethanol again.At first, mixture under constantly stirring, vacuumizing/inflated with nitrogen is to remove dissolved oxygen, then 70 ℃ of polymerizations 24 hours.After polyreaction finishes, in reactant impouring 200ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 5.6g and gather (N-NSC 11448-co-vinylformic acid) (PNIPAM-8), yield is 94%, molecular weight Mw=6.5 * 10 of PNIPAM-8
3G/mol, molecular weight dispersion coefficient PDI=1.95.The correlation parameter of PNIPAM-8 is seen table 1.
Instance 9: N-NSC 11448,1.20g methylacrylic acid and the 0.24g Diisopropyl azodicarboxylate of 4.80g are joined in the glass reaction bottle, add 40ml ethanol again.At first, mixture under constantly stirring, vacuumizing/inflated with nitrogen is to remove dissolved oxygen, then 70 ℃ of polymerizations 24 hours.After polyreaction finishes, in reactant impouring 120ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 5.7g and gather (N-NSC 11448-co-methylacrylic acid) (PNIPAM-9), yield is 96%, molecular weight Mw=2.39 * 10 of PNIPAM-9
4G/mol, molecular weight dispersion coefficient PDI=2.03.The correlation parameter of PNIPAM-9 is seen table 1.
Instance 10: N-NSC 11448,1.20g acrylic amide and the 0.24g Diisopropyl azodicarboxylate of 4.80g are joined in the glass reaction bottle, add 20ml ethanol again.At first, mixture under constantly stirring, vacuumizing/inflated with nitrogen is to remove dissolved oxygen, then 70 ℃ of polymerizations 24 hours.After polyreaction finishes, in reactant impouring 40ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 5.6g and gather (N-NSC 11448-co-acrylic amide) (PNIPAM-10), yield is 94%, molecular weight Mw=3.31 * 10 of PNIPAM-10
4G/mol, molecular weight dispersion coefficient PDI=2.05.The correlation parameter of PNIPAM-10 is seen table 1.
Instance 11: N-NSC 11448,1.20g pyrrolidone and the 0.12g Diisopropyl azodicarboxylate of 4.80g are joined in the glass reaction bottle, add 10ml ethanol again.At first, mixture under constantly stirring, vacuumizing/inflated with nitrogen is to remove dissolved oxygen, then 70 ℃ of polymerizations 24 hours.After polyreaction finishes, in reactant impouring 30ml ice ether, obtain white depositions.Filter and collect white depositions, with white depositions vacuum-drying at room temperature 1 day, obtain 5.6g and gather (N-NSC 11448-co-pyrrolidone) (PNIPAM-11), yield is 94%, molecular weight Mw=4.86 * 10 of PNIPAM-11
4G/mol, molecular weight dispersion coefficient PDI=1.86.The correlation parameter of PNIPAM-11 is seen table 1.
Table 1. is by the structure directing agent of instance 1～11 preparation.
Instance 12: under room temperature and agitation condition, earlier the 1.0mol/l aqueous sulfuric acid of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 25 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-1, its sample optical photograph is seen Fig. 2, and the SEM photo is seen Fig. 4, and the TEM photo is seen Fig. 6).SiO
2-1 mean pore size is 3.4nm, and pore volume is 0.33cm
3/ g, specific surface area is 611m
2/ g (its N
2The adsorption/desorption curve is seen Fig. 8).SiO
2-1 correlation parameter is seen table 2.
Instance 13: under room temperature and agitation condition, the 13g/l sodium silicate aqueous solution that earlier aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to 400ml makes among the pH ≈ 5.0 of mixing solutions, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 80 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-2).SiO
2-2 mean pore size is 3.9nm, and pore volume is 0.79cm
3/ g, specific surface area is 893m
2/ g.SiO
2-2 correlation parameter is seen table 2.
Instance 14: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-3, its sample photo is seen Fig. 3, and the SEM photo is seen Fig. 5, and the TEM photo is seen Fig. 7).SiO
2-3 mean pore size is 4.6nm, and pore volume is 0.86cm
3/ g, specific surface area is 906m
2/ g (its N
2The adsorption/desorption curve is seen Fig. 9).SiO
2-3 correlation parameter is seen table 2.
Instance 15: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63mL is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 150 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses 5ml ethanol (room temperature) washing more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-4).SiO
2-4 mean pore size is 5.0nm, and pore volume is 0.92cm
3/ g, specific surface area is 958m
2/ g.SiO
2-4 correlation parameter is seen table 2.
Instance 16: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/L of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 25g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-5).SiO
2-5 mean pore size is 8.2nm, and pore volume is 1.05cm
3/ g, specific surface area is 558m
2/ g.SiO
2-5 correlation parameter is seen table 2.
Instance 17: under room temperature and agitation condition, earlier the 1.0mol/l aqueous sulfuric acid of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 15g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-6).SiO
2-6 mean pore size is 6.2nm, and pore volume is 1.00cm
3/ g, specific surface area is 616m
2/ g.SiO
2-6 correlation parameter is seen table 2.
Instance 18: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 1.7g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-7).SiO
2-7 mean pore size is 5.2nm, and pore volume is 0.92cm
3/ g, specific surface area is 731m
2/ g.SiO
2-7 correlation parameter is seen table 2.
Instance 19: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 62ml is added drop-wise to the pH ≈ 7.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-8).SiO
2-8 mean pore size is 5.6nm, and pore volume is 0.88cm
3/ g, specific surface area is 705m
2/ g.SiO
2-8 correlation parameter is seen table 2.
Instance 20: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 64ml is added drop-wise to the pH ≈ 4.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-9).SiO
2-9 mean pore size is 6.0nm, and pore volume is 0.84cm
3/ g, specific surface area is 683m
2/ g.SiO
2-9 correlation parameter is seen table 2.
Instance 21: under room temperature and agitation condition, earlier the aqueous hydrochloric acid of the 1.0mol/l of 125ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-10).SiO
2-10 mean pore size is 4.9nm, and pore volume is 0.92cm
3/ g, specific surface area is 882m
2/ g.SiO
2-10 correlation parameter is seen table 2.
Instance 22: under room temperature and agitation condition, earlier the phosphate aqueous solution of the 0.5mol/l of 20ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 6g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-5 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ condition, obtain 1.2g white powder mesoporous silicon oxide (SiO at last
2-11).SiO
2-11 mean pore size is 4.0nm, and pore volume is 0.76cm
3/ g, specific surface area is 768m
2/ g.SiO
2-11 correlation parameter is seen table 2.
Instance 23: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-1 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-12).SiO
2-12 mean pore size is 2.4nm, and pore volume is 0.27cm
3/ g, specific surface area is 545m
2/ g.SiO
2-12 correlation parameter is seen table 2.
Instance 24: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-2 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-13).SiO
2-13 mean pore size is 2.6nm, and pore volume is 0.44cm
3/ g, specific surface area is 785m
2/ g.SiO
2-13 correlation parameter is seen table 2.
Instance 25: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-3 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-14).SiO
2-14 mean pore size is 5.2nm, and pore volume is 0.66cm
3/ g, specific surface area is 613m
2/ g.SiO
2-14 correlation parameter is seen table 2.
Instance 26: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-4 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-15).SiO
2-15 mean pore size is 6.6nm, and pore volume is 0.69cm
3/ g, specific surface area is 523m
2/ g.SiO
2-15 correlation parameter is seen table 2.
Instance 27: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-6 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-16).SiO
2-16 mean pore size is 5.8nm, and pore volume is 0.94cm
3/ g, specific surface area is 643m
2/ g.SiO
2-16 correlation parameter is seen table 2.
Instance 28: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-7 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-17).SiO
2-17 mean pore size is 5.3nm, and pore volume is 0.90cm
3/ g, specific surface area is 670m
2/ g.SiO
2-17 correlation parameter is seen table 2.
Instance 29: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-8 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-18).SiO
2-18 mean pore size is 8.1nm, and pore volume is 1.01cm
3/ g, specific surface area is 556m
2/ g.SiO
2-18 correlation parameter is seen table 2.
Instance 30: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-9 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-19).SiO
2-19 mean pore size is 9.8nm, and pore volume is 1.13cm
3/ g, specific surface area is 520m
2/ g.SiO
2-19 correlation parameter is seen table 2.
Instance 31: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-10 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-20).SiO
2-20 mean pore size is 9.5nm, and pore volume is 0.95cm
3/ g, specific surface area is 542m
2/ g.SiO
2-20 correlation parameter is seen table 2.
Instance 32: under room temperature and agitation condition, earlier the aqueous sulfuric acid of the 1.0mol/l of 63ml is added drop-wise to the pH ≈ 5.0 that makes mixing solutions in the 13g/l sodium silicate aqueous solution of 400ml, immediately it is joined in the PNIPAM-11 aqueous solution of 5g/l of 500ml then; Obtain white depositions, continue to stir 1 hour, with reactant transfer in hydrothermal reaction kettle; Under 100 ℃ temperature, left standstill aging 24 hours; Again reactant is naturally cooled to room temperature, filter, collect white depositions.Earlier white depositions is lower than 30 ℃ water logging bubble washing 2～3 times with 20ml, uses the 5ml washing with alcohol more once, with the white precipitate of collecting vacuum-drying 24 hours under 30 ℃ temperature, obtain 2.4g white powder mesoporous silicon oxide (SiO at last
2-21).SiO
2-21 mean pore size is 10.6nm, and pore volume is 1.05cm
3/ g, specific surface area is 502m
2/ g.SiO
2-21 correlation parameter is seen table 2.
Table 2. is by the mesoporous silicon oxide of instance 12～33 preparations.
Claims (5)
1. one kind prepares the method for mesoporous silicon oxide with the temperature sensing polymer structure directing agent, it is characterized in that comprising the steps: one, through the polymerization method of radical polymerization synthetic have temperature sensitive property gather (N-NSC 11448) or based on the structure directing agent of the hydrophilic copolymers that gathers (N-NSC 11448) as the preparation mesoporous silicon oxide; Two, the pH value with certain density sodium silicate aqueous solution is adjusted to slightly acidic; Under room temperature and agitation condition; The acidifying sodium silicate aqueous solution is joined in the homopolymer or the aqueous solution based on the hydrophilic copolymers that gathers (N-NSC 11448) that gathers (N-NSC 11448); Obtain white depositions immediately, continue to stir 1 hour; Three, with reactant transfer in hydrothermal reaction kettle, left standstill at a certain temperature aging 24 hours; Four, reactant is naturally cooled to room temperature; Filter, collect white depositions, the water logging bubble of white depositions with 0～30 ℃ washed 2～3 times; Again once, at last the white precipitate of collecting vacuum-drying under 30 ℃ condition was promptly obtained mesoporous silicon oxide in 24 hours with washing with alcohol;
As the gathering of structure directing agent (N-NSC 11448) or based on the weight-average molecular weight Mw of the hydrophilic copolymers that gathers (N-NSC 11448) at 3000-300000g/mol, molecular weight dispersion coefficient PDI is between 1.05-5.00;
As structure directing agent based on the hydrophilic copolymers that gathers (N-NSC 11448) for gathering (N-NSC 11448-co-vinylformic acid), gather (N-NSC 11448-co-methylacrylic acid), gather (N-NSC 11448-co-acrylic amide), gather (N-NSC 11448-co-pyrrolidone) or gathering (N-NSC 11448-co-vinyl alcohol);
Step 2 is used gathers (N-NSC 11448) or is 1～15g/L based on the concentration of the hydrophilic copolymers structure directing agent that gathers (N-NSC 11448);
The concentration of the sodium silicate aqueous solution that step 2 is used is 1～15g/L;
The structure directing agent that step 2 is required and the mass ratio of silicon-dioxide are between 1: 5～5: 1;
The needed aging temperature of step 3 is 25～150 ℃.
2. according to claim 1ly a kind ofly prepare the method for mesoporous silicon oxide with the temperature sensing polymer structure directing agent, the concentration that it is characterized in that the sodium silicate aqueous solution that step 2 is used is 6～13g/L.
3. according to claim 1ly a kind ofly prepare the method for mesoporous silicon oxide, it is characterized in that it is hydrochloric acid, sulfuric acid, perchloric acid, Hydrogen bromide or nitric acid that step 2 is regulated the used acid of sodium silicate aqueous solution pH with the temperature sensing polymer structure directing agent.
4. according to claim 1ly a kind ofly prepare the method for mesoporous silicon oxide with the temperature sensing polymer structure directing agent, the pH value that it is characterized in that the sodium silicate solution that step 2 is used is 4.0～7.0.
5. according to claim 1ly a kind ofly prepare the method for mesoporous silicon oxide, it is characterized in that the needed aging temperature of step 3 is 80～150 ℃ with the temperature sensing polymer structure directing agent.
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