CN100999317A - Nitrogen-containing ordered mesopore carbon and its synthesis method - Google Patents
Nitrogen-containing ordered mesopore carbon and its synthesis method Download PDFInfo
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Abstract
This invention discloses a new order mesoporous carbon that contains nitrogen and its composition method and initial application in adsorbing domain. Composition method: make solubilis resin and organic predecessor containing nitrogen for reaction in organic solvent, utilize predecessor and nonionic wetting agent to carry out self assembly, get resin-nonionic wetting agent composite containing nitrogen, remove surface acting agent by calcinating in inert atmosphere, carbonize, get order mesoporous carbon containing nitrogen; or carbonize at high temperature resin-nonionic wetting agent composite containing nitrogen, get order mesoporous carbon containing nitrogen. Pore diameter of prepared mesoporous carbon is 2.0-6.0nm, bore is 0.10-1.00 cu cm / g. Specific surface area is 500-1200sq m/g. C/N molar ratio is 100:0.20-100:10.00. It can be used as adsorbing substance of phenolic compounds in waste liquids. It has extensive application prospect in catalytic action, heavy metal ion, and colorant molecular adsorption and electrode materials.
Description
Technical field
The invention belongs to technical field of material, that be specifically related to is a kind of novel nitrogen-containing ordered mesoporous carbon material and preparation method and in the application of adsorbing domain.
Background technology
Meso-porous carbon material has caused people's extensive concern, this is to see the mesopore orbit of ordered structure, homogeneous because this class material has to be situated between on the one hand, high-specific surface area and large pore volume, therefore the characteristic that has carbon material itself on the other hand is in absorption, catalysis, separation, electrochemical electrode, photoelectric device, protein adsorption and the field such as separate wide purposes is arranged.Further the functional mesoporous carbon material of functionalization acquisition will represent more excellent performance, expands practical application area.But than traditional mesopore silicon oxide, the unreactiveness of carbon material surface makes its functionalization be difficult to carry out.Several frequently seen functional method is at present: the direct carbonization of (1) organic mesopore silicon oxide; (2) surface treatment; (3) nanometer teeming practice.
By the organosilane and the supramolecule template synthetic ordered mesoporous material of bridging, promptly periodic mesoporous organic silicon oxide material abbreviates PMOs (Periodic Mesoporous Organosilicas) as, is representing the organic-inorganic nano component of a class novelty.Its major advantage is that the content of (1) organo-functional group can increase greatly, and linking to each other with organic group of Siliciumatom 100% only can reach 25% and the connection rate of the terminal organic group of above-mentioned mesopore silicon oxide is the highest, and often being situated between this moment, it is very low to see the degree of order; (2) organic group is evenly distributed in the middle of the skeleton, thereby can effectively avoid the aperture blocking problem, simultaneously, can effectively improve the engagement capacity of itself and adsorptive; (3) organic group is introduced the hole within the walls, can regulate the physics and the chemical property of material well.Further carbonization can obtain the functionalized group of retained part, the polycomponent hybrid material of silicon oxide and carbon.But, in this type of material, use expensive bridging organosilane, and because the restriction of this one type of silane, the functionalization component of introducing is more single.This method is not suitable for the mesoporous material except that the oxidation silicon components yet.
In surface treatment method, can adopt strong oxidizer or strong reductant that oxidation or reduction processing are carried out in the surface, introduce the functionalization component.The method that also can adopt fluorine gas to purge is fluoridized carbon material surface.But, these method steps complexity, difficult control.
The functionalization of ordered mesopore carbon can also adopt the method for nanometer casting, and this method is mainly adopted in the preparation of present nitrogenous ordered mesopore carbon.Promptly prepare ordered mesoporous silica dioxide material (as SBA-15, MCM-48 etc.) earlier, be that hard template is poured into nitrogenous carbon source (as: quadrol/tetracol phenixin, polypyrrole, acetonitrile, polyacrylonitrile etc.) in mesopore orbit with this type of material again, carry out high temperature cabonization, remove silicon oxide by hydrofluoric acid or sodium hydroxide solution dissolving at last, obtain the anti-phase nitrogenous meso-porous carbon material that duplicates the template mesoscopic structure.This class methods preparation process is loaded down with trivial details, and the cycle is long.Therefore, press for a kind of method, obtain introducing in the mesoporous carbon functionalization group in the tensio-active agent self-assembly.
Summary of the invention
At the deficiency that prior art exists, one of problem that the present invention need solve provides a kind of novel nitrogenous ordered mesoporous carbon material;
Two of the problem that the present invention need solve provides the synthetic method of above-mentioned nitrogenous ordered mesoporous carbon material;
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of nitrogenous ordered mesopore carbon, its aperture are 2.0～6.0nm, and pore volume is 0.10～1.00cm
3/ g, specific surface area is 500～1200m
2/ g, carbon nitrogen mol ratio is 100: 0.20～100: 10.00.
The synthetic method of this nitrogenous ordered mesopore carbon comprises the steps:
(1) at room temperature, the soluble resin presoma is dispersed in the organic solvent, adds nitrogenous organic precursors, react settled solution; The mass ratio of nitrogenous organic precursors and soluble resin presoma is 0～1.00, and the reaction times is 1～5 hour;
(2) nonionogenic tenside is dissolved in the organic solvent settled solution;
(3) then with two kinds of solution mixing of (1) and (2) step, stir and make solvent evaporates; After treating that solvent evaporates is intact, low-temperature curing, gained solid product resinamines-nonionogenic tenside matrix material low-temperature bake under inert atmosphere, the low-temperature bake temperature is 350～500 ℃; Temperature rise rate is 1～5 ℃/min.Obtain nitrogenous ordered mesoporous polymer,, obtain the nitrogenous ordered mesopore carbon of the present invention, perhaps resinamines-one step of nonionogenic tenside matrix material high temperature cabonization is obtained the nitrogenous ordered mesopore carbon of the present invention the further carbonization of nitrogenous ordered mesoporous polymer.
Low-temperature curing temperature described in above-mentioned (3) step is 80 ℃～120 ℃, and the time is 12～72 hours.
Inert atmosphere can be a nitrogen described in above-mentioned (3) step, also can be argon gas.
The carbonization temperature that further carbonization gets nitrogenous ordered mesopore carbon under inert atmosphere of nitrogenous ordered mesoporous polymer described in above-mentioned (3) step is 600～900 ℃, and roasting time is 4～10 hours, and temperature rise rate is 1～5 ℃/min.
Resinamines described in above-mentioned (3) step-nonionogenic tenside matrix material at the carbonization process that next footwork high temperature cabonization of inert atmosphere gets nitrogenous ordered mesopore carbon was: 350～500 ℃ of roastings 5～10 hours, be warming up to 600～900 ℃ then, roasting 4～10 hours, temperature rise rate are 1～5 ℃/min.
Reaction mechanism of the present invention is: in organic solvent, soluble resin and nitrogenous organic precursors react, utilize organic-organic self-assembly of this presoma and nonionogenic tenside to obtain resinamines-nonionogenic tenside matrix material then, low-temperature bake is removed tensio-active agent under the inert atmosphere, promptly obtain nitrogenous ordered mesoporous polymer, further carbonization obtains the nitrogenous ordered mesopore carbon of corresponding construction; The resinamines that perhaps self-assembly obtained-one step of nonionogenic tenside matrix material high temperature cabonization obtains nitrogenous ordered mesopore carbon.
Used organic solvent is one or more in alcohols, benzene class, tetrahydrofuran (THF), ether, chloroform or the methylene dichloride etc., the present invention utilizes the volatilization of organic solvent to induce the nonionogenic tenside self-assembly to form the meso-hole structure of high-sequential, organic solvent can be a protic solvent, as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, tetrahydrofuran (THF) or the like, also can be non-protonic solvent, as benzene, toluene, ether, chloroform, methylene dichloride etc.
Used soluble resin can be one or more in resol, urea-formaldehyde resin, polyimide, polyacrylamide, the polyacrylonitrile etc., and their molecular weight is 200～5000; Used nitrogenous organic precursors can be one or more in aniline, Metha Amino Phenon, the p-aminophenol etc.
Among the present invention, used nonionogenic tenside is tensio-active agents such as polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or triblock copolymer.As C
nH
2n+1EO
m, EO
nPO
mEO
n, EO
nBO
mEO
n, EO
nBO
m, EO
nPO
mDeng.
Among the present invention, used nonionogenic tenside mainly includes Brij35 (C
12H
25EO
23), Brij56 (C
16H
33EO
10), Brij76 (C
18H
37EO
10), P123 (EO
20PO
70EO
20), F127 (EO
106PO
70EO
106), F108 (EO
132PO
50EO
132) etc.The duct spatial symmetry of products therefrom can be two-dimentional hexagonal structure, and spacer comprises the p6mm structure, or three-dimensional cubic structure, and spacer comprises structure
Structure.
Among the present invention, adopt the precursor of soluble resin as the synthetic macromolecule mesoporous material, it is lower at the initial reaction stage molecular weight, can well be dissolved in organic solvent, forms the homogeneous system with organic solvent, nonionogenic tenside.Solvent evaporates is warming up to temperature of reaction after inducing mesoscopic structure to form, and the soluble resin presoma can be further crosslinked, finally obtains insoluble infusible macromolecular material.Used macromolecular material is compared with nonionogenic tenside has higher thermostability or chemical stability.
Among the present invention, used soluble resin can be business-like polymer presoma, also can be homemade polymer oligopolymer presoma.They can be in resol, urea-formaldehyde resin, polyimide, polyacrylamide, the polyacrylonitrile etc. one or more.The molecular weight of presoma is generally between 200～5000.
Among the present invention, used nitrogenous organic precursors can be one or more in aniline, Metha Amino Phenon, the p-aminophenol etc.
The present invention is synthesizing ordered by organic one organic self-assembly, have continuously, the mesoporous carbon of open pore passage structure.For further functionalization, nitrogenous carbon source is introduced system, induce organic-organic self-assembling method by solvent evaporates, prepare nitrogenous ordered mesopore carbon.This type of material has open skeleton structure, and is applied to the absorption of target contaminant phenol first.
The preparation method of mesoporous material of the present invention is simple, and cost is low.The nitrogenous ordered mesopore carbon that makes by the present invention contains nitrogen-atoms in skeleton, and the duct high-sequential, the specific surface area height, and the aperture is big, and pore volume is big.These novel nitrogenous mesoporous materials have good adsorptive power in the processing of phenolic wastewater, under the same conditions, the phenol adsorptive capacity of gac is 50～200mg/g, and the phenol adsorptive capacity of nitrogenous mesoporous carbon is 150～500mg/g.Simultaneously, this nitrogenous ordered mesoporous material has broad application prospects at aspects such as catalysis, the absorption of adsorbing heavy metal ions in wastewater, dye molecule and electrode materialss.
Description of drawings
Fig. 1 has characteristic X-ray diffraction (XRD) collection of illustrative plates of the nitrogenous ordered mesoporous carbon material of two dimension six side p6mm structures for the present invention.
Fig. 2 has the feature nitrogen adsorption-desorption isotherm figure of the nitrogenous ordered mesoporous carbon material of two dimension six side p6mm structures for the present invention.
Fig. 3 has the TEM figure of the nitrogenous ordered mesopore carbon of two dimension six side p6mm structures for the present invention.
Fig. 4 has three-dimensional cubic for the present invention
Characteristic X-ray diffraction (XRD) collection of illustrative plates of the nitrogenous ordered mesopore carbon of structure.
Fig. 5 has three-dimensional cubic for the present invention
Feature nitrogen adsorption-desorption isotherm the figure of the nitrogenous ordered mesopore carbon of structure.
Fig. 6 has three-dimensional cubic for the present invention
The TEM figure of the nitrogenous ordered mesopore carbon of structure.
Fig. 7 is the phenol absorption spirogram of mesoporous carbon of the present invention.
Wherein:
Fig. 1 stirs and obtains solution A after 2 hours for the 0.02g Metha Amino Phenon is dissolved in the 5.00g soluble resin presoma.0.61gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stir and pour in the culture dish after 30 minutes, after treating that solvent evaporates is intact, 100 ℃ of low-temperature curings, be 48 hours set time, gets resinamines-nonionogenic tenside matrix material, 350 ℃ of roastings are 5 hours under nitrogen atmosphere, obtain nitrogenous mesoporous polymer, 900 ℃ of roastings are 5 hours then, and carbonization gets characteristic X-ray diffraction (XRD) collection of illustrative plates of nitrogenous ordered mesoporous carbon material.
Fig. 2 stirs and obtains solution A after 2 hours for the 0.02g Metha Amino Phenon is dissolved in the 5.00g soluble resin presoma.0.61gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stir and pour in the culture dish after 30 minutes, after treating that solvent evaporates is intact, 100 ℃ of low-temperature curings, be 48 hours set time, gets resinamines-nonionogenic tenside matrix material, 350 ℃ of roastings are 5 hours under nitrogen atmosphere, obtain nitrogenous mesoporous polymer, 900 ℃ of roastings are 5 hours then, and carbonization gets the feature nitrogen adsorption-desorption isotherm figure of nitrogenous ordered mesoporous carbon material.
Fig. 3 stirs and obtains solution A after 3 hours for the 0.05g Metha Amino Phenon is dissolved in the 5.00g soluble resin presoma.0.61gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stir and pour in the culture dish after 60 minutes, after treating that solvent evaporates is intact, 90 ℃ of low-temperature curings, be 48 hours set time, get resinamines-nonionogenic tenside matrix material, 900 ℃ of roastings of next footwork of nitrogen atmosphere 5 hours, carbonization got the TEM figure of nitrogenous ordered mesoporous carbon material.
Fig. 4 stirs and obtains solution A after 2 hours for the 0.02g Metha Amino Phenon is dissolved in the 5.00g soluble resin presoma.0.42gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stir and pour in the culture dish after 10 minutes, after treating that solvent evaporates is intact, 90 ℃ of low-temperature curings, be 32 hours set time, get resinamines-nonionogenic tenside matrix material, 900 ℃ of roastings of next footwork of argon gas atmosphere 6 hours, carbonization obtained characteristic X-ray diffraction (XRD) collection of illustrative plates of nitrogenous ordered mesopore carbon.
Fig. 5 stirs and obtains solution A after 2 hours for the 0.02g Metha Amino Phenon is dissolved in the 5.00g soluble resin presoma.0.42gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stir and pour in the culture dish after 10 minutes, after treating that solvent evaporates is intact, 90 ℃ of low-temperature curings, be 32 hours set time, get resinamines-nonionogenic tenside matrix material, 900 ℃ of roastings of next footwork of argon gas atmosphere 6 hours, carbonization obtained the feature nitrogen adsorption-desorption isotherm figure of nitrogenous ordered mesopore carbon.
Fig. 6 stirs and obtains solution A after 3 hours for the 0.05g Metha Amino Phenon is dissolved in the 5.00g soluble resin presoma.0.42gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stir and pour in the culture dish after 30 minutes, after treating that solvent evaporates is intact, 100 ℃ of low-temperature curings, be 24 hours set time, get resinamines-nonionogenic tenside matrix material, 900 ℃ of roastings of next footwork of nitrogen atmosphere 6 hours, carbonization obtained the TEM figure of nitrogenous ordered mesopore carbon.
Fig. 7 is for being that 0.05 nitrogenous meso-porous carbon material is put in the 100mL exsiccant iodine flask with the mass ratio of Metha Amino Phenon and soluble resin presoma, put into the phenol solution that 40mL concentration is 0.564mg/mL, 25 ℃ of constant temperature vibrations were adsorbed 24 hours, with its phenol concentration of uv-absorbing photometer measurement, calculate phenol adsorptive capacity gained figure.
Embodiment
To further describe the present invention by specific embodiment below, enumerating these examples only is in order to set forth rather than limit by any way the present invention.
Example 1
The preparation of soluble resin precursor solution is put in 8.00g phenol in the three-necked flask, and 42 ℃ of heating in water bath make phenol be transparent liquid, and the sodium hydroxide solution (take by weighing 0.34gNaOH, add 1.36g distilled water) of preparation 20% slowly splashes in the phenol liquid.After 10 minutes, adding quality percentage composition is 37% formaldehyde solution 14.16g, and 70 ℃ were refluxed 1 hour, were cooled to room temperature, regulated pH to neutrality with 2mol/L hydrochloric acid.Underpressure distillation under 45 ℃～50 ℃ conditions, be cooled to room temperature after, be made into 20% ethanol or diethyl ether solution.
Example 2
The 0.02g Metha Amino Phenon is dissolved in the soluble resin presoma that obtains in the 5.00g example 1, stirs and obtain solution A after 2 hours.0.61gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stirred 30 minutes.Evenly be laid on this mixed solution in the culture dish then, room temperature was placed 7 hours, was transferred to 100 ℃ of baking ovens at last, after 24 hours, with product 350 ℃ of roastings 5 hours under nitrogen atmosphere, obtain nitrogenous mesoporous polymer, 900 ℃ of roastings are 5 hours then, obtain nitrogenous meso-porous carbon material, as shown in Figure 1, XRD spectra proves that this material has two-dimentional hexagonal structure (spacer p6mm), and the aperture is at 4.3nm, and pore volume is 0.63cm
3/ g, specific surface area is 1177m
2/ g, its N
2The adsorption desorption thermoisopleth belongs to IV type (as shown in Figure 2).Ultimate analysis proves that carbon nitrogen mol ratio is 100: 0.85 in the nitrogenous mesoporous carbon.
Example 3
The 0.05g Metha Amino Phenon is dissolved in the diethyl ether solution of the soluble resin that obtains in the 5.00g example 1, stirs and obtain A solution after 2 hours.0.61gF127 is dissolved in the 8.00g ether, stirs and got B solution in 10 minutes.Mix A, B solution, stirred 60 minutes.Evenly be laid on this mixed solution in the culture dish then; room temperature was placed 7 hours; be transferred to 120 ℃ of baking ovens at last; after 24 hours; product in the roasting 6 hours respectively of 600 ℃ and 900 ℃ under nitrogen protection, is obtained nitrogenous meso-porous carbon material, all have two-dimentional hexagonal structure (spacer p6mm); the aperture is respectively 5.2nm and 4.0nm, and pore volume is respectively 0.42cm
3/ g and 0.43cm
3/ g, specific surface area is respectively 705m
2/ g and 890m
2/ g.
Example 4
The 0.02g Metha Amino Phenon is dissolved in the soluble resin presoma that obtains in the 5.00g example 1, stirs and obtain A solution after 2 hours.0.42gF127 is dissolved in the 8.00g dehydrated alcohol, stirs and got B solution in 10 minutes.Mix A, B solution, stirred 10 minutes.Then this mixed solution evenly is laid in the culture dish, room temperature was placed 7 hours, was transferred to 90 ℃ of baking ovens at last, after 32 hours, with product 900 ℃ of roastings 6 hours under argon gas atmosphere, obtain nitrogenous meso-porous carbon material, the meso-porous carbon material of gained has three-dimensional cubic structure (spacer
As shown in Figure 4), the aperture is 3.9nm, and pore volume is 0.31cm
3/ g, specific surface area is 709m
2/ g, its N
2The adsorption desorption thermoisopleth belongs to IV type (as shown in Figure 5).
Example 5
Gac is put in the 100mL exsiccant iodine flask, puts into the phenol solution that 40mL concentration is 0.564mg/mL, 25 ℃ of constant temperature vibrations were adsorbed 24 hours, filtered, and got clear liquid 1mL and were diluted to the 100mL aqueous solution, with its phenol concentration of uv-absorbing photometer measurement.During balance, loading capacity Qe (mg/mL) with the pass of equilibrium concentration is: Qe=(Co-Ce) V/ resin gram number.In the formula: the initial concentration of Co-phenol (mg/mL), the concentration of phenol (mg/mL) during the Ce-balance, the cumulative volume of V-solution (mL).Calculate to such an extent that its phenol adsorptive capacity is 50mG/g, as shown in Figure 7.
Example 6
With the mass ratio of Metha Amino Phenon and soluble resin presoma is that 0.05 nitrogenous mesoporous carbon is put in the 100mL exsiccant iodine flask, put into the phenol solution that 40mL concentration is 0.564mg/mL, 25 ℃ of constant temperature vibrations were adsorbed 24 hours, filter, get clear liquid 1mL and be diluted to the 100mL aqueous solution, with its phenol concentration of uv-absorbing photometer measurement.Calculating its phenol adsorptive capacity by example 5 is 288mg/g, as shown in Figure 7.
Claims (12)
1, a kind of nitrogenous ordered mesopore carbon is characterized in that, the aperture of nitrogenous ordered mesopore carbon is 2.0～6.0nm, and pore volume is 0.10～1.00cm
3/ g, specific surface area is 500～1200m
2/ g, carbon nitrogen mol ratio is 100: 0.20～100: 10.00.
2, the synthetic method of the described nitrogenous ordered mesopore carbon of claim 1 comprises the steps:
(1) at room temperature, the soluble resin presoma is dispersed in the organic solvent, adds nitrogenous organic precursors, react settled solution; The mass ratio of nitrogenous organic precursors and soluble resin presoma is 0～1.00, and the reaction times is 1～5 hour;
(2) nonionogenic tenside is dissolved in the organic solvent settled solution;
(3) then with two kinds of solution mixing of (1) and (2) step, stir and make solvent evaporates; After treating that solvent evaporates is intact, low-temperature curing, gained solid product resinamines one nonionogenic tenside matrix material low-temperature bake under inert atmosphere, can get nitrogenous ordered mesoporous polymer, further carbonization, obtain the nitrogenous ordered mesopore carbon of the present invention, perhaps resinamines one nonionogenic tenside matrix material one step high temperature cabonization is obtained the nitrogenous ordered mesopore carbon of the present invention.
3, synthetic method according to claim 2 is characterized in that: the low-temperature curing temperature in described (3) step is 80～120 ℃, and the time is 12～72 hours.
4, synthetic method according to claim 2 is characterized in that: the low-temperature bake temperature in described (3) step is 350～500 ℃; Temperature rise rate is 1～5 ℃/min.
5, synthetic method according to claim 2 is characterized in that: the inert atmosphere that roasting is adopted in described (3) step is nitrogen or argon gas.
6, synthetic method according to claim 2, it is characterized in that: the carbonization temperature that further carbonization gets nitrogenous ordered mesopore carbon under inert atmosphere of nitrogenous ordered mesoporous polymer described in (3) step is 600～900 ℃, roasting time is 4～10 hours, and temperature rise rate is 1～5 ℃/min.
7, synthetic method according to claim 2, it is characterized in that: resinamines described in (3) step-nonionogenic tenside matrix material at the carbonization process that next footwork high temperature cabonization of inert atmosphere gets nitrogenous ordered mesopore carbon was: 350～500 ℃ of roastings 5～10 hours, be warming up to 600～900 ℃ then, roasting 4～10 hours, temperature rise rate are 1～5 ℃/min.
8, according to any described synthetic method of claim of claim 2-7, it is characterized in that: described soluble resin is one or more mixtures in resol, urea-formaldehyde resin, polyimide, polyacrylamide, the polyacrylonitrile, and their molecular weight is 200～5000.
9, according to any described synthetic method of claim of claim 2-7, it is characterized in that: described nitrogenous organic precursors is one or more the mixture in aniline, Metha Amino Phenon, the p-aminophenol.
10, according to any described synthetic method of claim of claim 2-7, it is characterized in that: described nonionogenic tenside is one or more mixtures in polyethylene oxide-poly(propylene oxide), polyethylene oxide-polybutylene oxide, alkane-polyethylene oxide type diblock or the triblock copolymer tensio-active agent.
11, synthetic method according to claim 10 is characterized in that: described nonionogenic tenside is C
nH
2n+1EO
m, EO
nPO
mEO
n, EO
nBO
mEO
n, EO
nBO
m, EO
nPO
mOne or more mixtures neutralize.
12, synthetic method according to claim 11 is characterized in that: described nonionogenic tenside is C
12H
25EO
23, C
16H
33EO
10, C
18H
37EO
10, EO
20PO
70EO
20, EO
106PO
70EO
106, EO
132PO
50EO
132In one or more mixtures.
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