CN101733152B - Magnetic cation exchange resin catalyzer and preparation method and application thereof - Google Patents
Magnetic cation exchange resin catalyzer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a magnetic cation exchange resin catalyzer and a preparation method and application thereof. In the method, nanometer magnetic metal oxide and long-chain fatty acid are mixed in the water the pH of which is 9-12, the pH is regulated to 4-5, and modified nanometer magnetic particulate is obtained after the nanometer magnetic metal oxide and the long-chain fatty acid react; monomer, evocating agents, crosslinking agents and pore-foaming agents are mixed with the modified nanometer magnetic particulate which accounts for 5-65% of the total weight of the monomer and the crosslinking agents, magnetic resin is obtained after polymerization, and the catalyzer is obtained through sulphur reaction of the magnetic resin. The catalyzer can be used for catalyzing olefin hydration reaction, ether hydrolysis reaction, esterification reaction, etherealization reaction, condensation reaction or aromatic hydrocarbon alkylation reaction in a magnetic reactor.
Description
Technical field
The present invention relates to a kind of magnetic cation exchange resin catalyzer.In particular, the present invention relates to a kind of macropore strong acid cation exchange resin catalyst with superparamagnetism.
Background technology
Magnetic stablizing bed as a kind of novel bed form, have the advantage of fixed bed and fluid bed concurrently, to compare with fluid bed, externally-applied magnetic field can effectively be controlled alternate back-mixing and particle leakage; Compare with fixed bed, magnetic stablizing bedly can use catalyst particle and be unlikely to cause too high pressure drop, voidage can make bed not produce channel and hot localised points uniformly.The prerequisite of using magnetic stablizing bed technology is that catalyst must have the magnetic response characteristic.
Storng-acid cation exchange resin can be used to replace homogeneous acid catalysts such as sulfuric acid, hydrochloric acid as solid acid catalyst; It is widely used in fields such as petrochemical industry, fine chemistry industry and pharmaceuticals industry, such as olefin hydration, ethers hydrolysis, esterification, etherificate, condensation and alkylating aromatic hydrocarbon etc.If can storng-acid cation exchange resin be given magnetic and be used for magnetic stablizing bedly, can give full play to both advantages.
In the prior art, the method for preparing magnetic ion exchange resin mainly is to mix with magnetic material with the polymer viscous solution, through disperseing, crosslinkedly processing spherical magnetic resin.In addition, also can be shaped at the magnetic powder surface aggregate with monomer or performed polymer obtains magnetic resin, and the magnetic resin ubiquity that obtains with said method the problem of acid and alkali resistance poor performance.Prior art mainly is to improve the covered effect of magnetic material through the adding auxiliary agent; From its preparation process; Auxiliary agent mainly combines with magnetic material through molecular separating force; Since molecular separating force relatively a little less than, cause the effect of its coating unsatisfactory, therefore in the process of sulfonation or hydrolysis, can cause the forfeiture of magnetic.CN 1680469 A disclose a kind of preparation method of magnetic ion exchange resin of nucleocapsid structure; It utilizes paraffin, pitch or stearic acid clad nano level magnetic particle to process magnetic nuclear, again nanometer or micron order reactive resin powder adherence is processed shell in magnetic nuclear outside.The prepared ion exchange resin of this method has only the appearance shell to have activity, and the acid amount that causes it to provide is limited, therefore is not suitable for catalytic field.CN1036526C discloses a kind of preparation of magnetic macroporous ion-exchange resin for adsorption, and this patent adopts stage feeding polymerization and the method that adds alkyl acid esters analog assistant to prepare the macroporous absorption ion exchange resin of coated magnetic material.From its disclosed performance indications, the magnetic resin that this method obtains is not suitable for being used as catalyst.
Magnetic resin material through prepared in various methods is mainly used in fields such as metal enrichment, sewage disposal, biochemistry, medical medicine at present, and its maximum application in industry is the middle organic molecule of purifying waste water.So far still no-trump magnetic resin material is used as the report that catalyst carries out Chemical Manufacture, and main cause is to the sulfonation of resin or acidification process magnetic particle is affected, and finally causes the magnetic of resin to disappear.
Summary of the invention
The technical problem that the present invention will solve provides a kind of preparation method of magnetic cation exchange resin catalyzer, and this method has good covered effect to magnetic particle, makes the catalyst after the sulfonation still keep strong magnetic.The present invention also provides resulting catalyst of this method and application thereof.
Method provided by the present invention may further comprise the steps:
(1) in the water of pH value 9～12, nano level magnetic metal oxide is mixed with LCFA, regulate pH value to 4～5, obtain the nano magnetic particle of modification after the reaction;
(2) with monomer, initator, crosslinking agent, pore-foaming agent with account for monomer and the modification magnetic particle of crosslinking agent gross weight 5～65% mixes, obtain magnetic resin after the polymerization, magnetic resin obtains final catalyst after sulfonating reaction.
The resulting magnetic cation exchange resin catalyzer of said method comprises macropore sulfonic acid polystyrene cationic ion-exchange resin and is embedded in the nano-scale magnetic metal oxide in the resin matrix structure that the weight ratio of the two is 1.5～20:1; Catalyst has superparamagnetism, and its specific saturation magnetization is 3.1～17.4, and acid capacity is 1.25～4.98.
The present invention also provides above-mentioned Application of Catalyst, with said catalyst catalyzed alkene hydration reaction, ethers hydrolysis, esterification, etherification reaction, condensation reaction or alkylation reaction of arene in the magnetic response device.
Compared with prior art, the present invention has the following advantages:
(1) preparation process of magnetic ion exchange resin and condition are most important as far as the covered effect of magnetic material, thereby the applicable field of performance and institute thereof of magnetic resin is produced critical impact.LCFA of the present invention forms firm combining with magnetic material through chemical bond, therefore is covered by easily in the skeleton structure of resin, thereby makes it behind sulfonation process, still can keep stronger magnetic.
(2) the present invention has adopted the terminal auxiliary agent that has unsaturated double-bond, through auxiliary agent and monomer copolymerization, magnetic material is coated more easily and is fixed on resin inside, thereby make the catalyst of the present invention have higher stability.
(3) catalyst of the present invention is milled to 300 orders; Can know through the photoelectron spectroscopy analysis; Particle surface after grinding does not have the Fe element or the small amounts of iron element is only arranged, and this explains that catalyst granules of the present invention is to be connected by the microballoon that inner packet is covered with magnetic material to form.
(4) the prepared catalyst of the present invention can be used in magnetic response device technology, and it can be regenerated in acidity or alkaline medium and keep structural stability.
Description of drawings
The preparation of Fig. 1 magnetic cation exchange resin catalyzer and structural representation.
Fig. 2 modified Nano magnetic particle content is the hysteresis curve of the magnetic nuclear resin of 30wt%.
The hysteresis curve of Fig. 3 magnetic cation exchange resin catalyzer.
The photoelectron spectroscopy of Fig. 4 magnetic cation exchange resin catalyzer
The specific embodiment
Specifically, method provided by the present invention can be carried out according to the following steps:
(1) nano level magnetic metal oxide is disperseed in water, regulate pH value to 9～12, under 40～55 ℃; Add LCFA with magnetic metal oxide mol ratio 0.1～0.6; Continue reaction 1.5～3h, regulate pH value to 4～5, be warming up to 55～75 ℃; React 1.5～3h, after magnetic separation, washing, drying, obtain the nano magnetic particle of modification;
(2) with monomer, initator, crosslinking agent, pore-foaming agent with account for monomer and the modification magnetic particle of crosslinking agent gross weight 5～65% evenly mixes; Behind 60～80 ℃ of pre-polymerization 5～40min; Add dispersant; Mode polymerization 6～14h that the employing stage heats up between 80 ℃ to 95 ℃ obtains magnetic resin after washing, drying, magnetic resin obtains final catalyst after sulfonating reaction.
Said magnetic metal oxide is preferably Fe
3O
4, γ-Fe
2O
3, CoFe
2O
4And MnFe
2O
4In one or more; Its particle diameter is preferably 3～50nm, more preferably 10～25nm.
Described LCFA is the carboxylic acid of C8～C24, is preferably the carboxylic acid that the carbochain end contains the C8～C24 of unsaturated double-bond, more preferably 10 hendecenoic acid, 11-lauroleic acid, 12-tridecylenic acid or 14-pentadecylenic acid.
In the step (1), the mol ratio of LCFA and magnetic metal oxide is preferably 0.1～0.3.
The described monomer of step (2) is selected from one or more in the substituted styrene of styrene, alkyl or halogen atom.The substituted styrene of alkyl or halogen atom comprises p-methylstyrene, to fluorobenzene ethene with to chlorostyrene etc.
The described initator of step (2) is peroxide initator or azo-initiator, preferred benzoyl peroxide or azo-bis-isobutyl cyanide; Initiator amount is 0.5～6% of monomer and a crosslinking agent gross weight.
The described crosslinking agent of step (2) is divinylbenzene, di isopropenylbenzene, divinyl toluene or divinyl xylenes.The consumption of crosslinking agent is 4～40% of monomer and a crosslinking agent gross weight, is preferably 8～25%.
Dispersant in the step (2) is the aqueous solution of water soluble polymer, and the consumption of dispersant is monomer and crosslinking agent cumulative volume 1～10 times, is preferably 2～4 times.Water soluble polymer is selected from one or more in gelatin, starch, bassora gum, polyvinyl alcohol, polyacrylate, methylcellulose and the CMC.Dispersant is preferably the aqueous solution of gelatin or polyvinyl alcohol, and the concentration of aqueous gelatin solution is 0.5～4wt%, and the concentration of polyvinyl alcohol water solution is 1～5wt%.
In the process of polymerization, also in suspension polymerization system, add dispersing aid usually so that the granularity of resin Archon is more even.Dispersing aid commonly used comprises styrene-maleic anhydride copolymer and the dimethyl diallyl ammonium chloride of polyacrylamide, Sodium Polyacrylate, saponification or ammoniumization etc.
Stage heating mode described in the step (2) is in the temperature range that limits, and with the uniform temperature gradient, progressively heats up and carries out polymerisation, and purpose is to make the crosslinking degree of copolymerization spherolite more even.
Pore-foaming agent described in the step (2) is alcohol, alkane, gasoline or Chinese wax etc.; Be preferably the fatty alcohol of C3～C8 or the alkane of C6～C20, like isopropyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, sec-butyl alcohol, isoamyl alcohol, tert-pentyl alcohol, neopentyl alcohol, n-amyl alcohol, n-hexyl alcohol, 2-ethyl-1-hexanol, isooctanol, normal heptane, normal octane, isooctane and n-decane etc.
In the step (2), the consumption of pore-foaming agent is 30～50% of monomer, crosslinking agent and a pore-foaming agent gross weight.
Magnetic cation exchange resin catalyzer provided by the present invention comprises macropore sulfonic acid polystyrene cationic ion-exchange resin and the nano-scale magnetic metal oxide that is embedded in the skeleton structure of resin, and the weight ratio of the two is 1.5～20:1; Catalyst has superparamagnetism, and its specific saturation magnetization is 3.1～17.4, and acid capacity is 1.25～4.98.
The weight ratio of macropore sulfonic acid polystyrene cationic ion-exchange resin and nano-scale magnetic metal oxide is preferably 2.3～4:1.
The specific saturation magnetization of catalyst is preferably 11.0～15.0, and acid capacity is preferably 3.50～4.50.
Described magnetic metal oxide is preferably Fe
3O
4, γ-Fe
2O
3, CoFe
2O
4And MnFe
2O
4In one or more; Its particle diameter is preferably 3～50nm, more preferably 10～25nm.
The degree of cross linking of described macropore sulfonic acid polystyrene cationic ion-exchange resin is 4～40%, is preferably 8～25%.
The particle size range of described magnetic cation exchange resin catalyzer is 50～1000 μ m.
The present invention also provides above-mentioned Application of Catalyst, with said catalyst catalyzed alkene hydration reaction, ethers hydrolysis, esterification, etherification reaction, condensation reaction or alkylation reaction of arene in the magnetic response device.
That described magnetic response device comprises is magnetic stablizing bed, magnetically fluidized bed and Magnetic suspension float bed.
Below further specify the present invention through embodiment.
The preparation of embodiment 1～8 explanation modification magnetic particle, the preparation of embodiment 9～12 explanation composite magnetic cationic ion-exchange resins.The alcoholysis degree of used polyvinyl alcohol is 77% among the embodiment, and inherent viscosity is 0.99.
Method (by the method described in Institutes Of Technology Of Nanjing's thesis for the doctorate-" preparation of magnetic nanoparticle and magnetic compound particles and the application study thereof ") according to the titration hydrolysis makes 4gFe
3O
4, still remain in the reaction solution, keep pH value 11, in the time of 50 ℃ of water-baths, drip the 0.7g 10 hendecenoic acid, mechanical agitation 1.5h; Drip the hydrochloric acid solution of 0.4mol/L, regulate pH value to 4.5, and be warming up to 70 ℃, keep 1.5h, reaction terminating.After the reaction system cooling, product is carried out magnetic separate, repeatedly with ethanol and distilled water washing, 40 ℃ of dried nanometer Fe to surperficial 10 hendecenoic acid modification
3O
4
With the 4g average grain diameter is the Fe of 20nm
3O
4, put into the there-necked flask of 2L, add 900mL distilled water, ultrasonic dispersing 2h is put in the water-bath and is warming up to 50 ℃ under the mechanical agitation, drips 0.4mol/LNaOH solution and regulates pH value to 10, in solution, drips 0.9g oleic acid again, keeps 1h; Drip the hydrochloric acid solution of 0.4mol/L, regulate pH value to 4, and be warming up to 70 ℃, keep 2h, reaction terminating.After the reaction system cooling, product is carried out magnetic separate, repeatedly with ethanol and distilled water washing, 40 ℃ of dried nanometer Fe to surperficial oleic acid modification
3O
4
Embodiment 3
Will be with the γ-Fe of thermal decomposition method preparation
2O
3Nano particle is (according to Synthesis of HighlyCrysta11ine and Monodisperse Maghemite Nanocrystallites without aSize-Selction Process, J.Am.Chem.Soc.2001,123; Method in 12798), pulverizes, put into the there-necked flask of 2L; Add 1000mL distilled water; Ultrasonic dispersing 3h is put in the water-bath and is warming up to 50 ℃ under the mechanical agitation, drips 0.4mol/LNaOH solution and regulates pH value to 10; In solution, drip the 0.8g dodecylic acid again, keep 2h; Drip the hydrochloric acid solution of 0.4mol/L, regulate pH value to 4.5, and be warming up to 70 ℃, keep 1.5h, reaction terminating.After the reaction system cooling, product is carried out magnetic separate, repeatedly with ethanol and distilled water washing, 40 ℃ of dried nanometer γ-Fe to surperficial dodecylic acid modification
2O
3
Method according to embodiment 1 makes 5gFe
3O
4, still remain in the reaction solution, keep pH value 12, in the time of 50 ℃ of water-baths, drip the 1g linoleic acid, mechanical agitation 1.5h; Drip the hydrochloric acid solution of 0.4mol/L, regulate pH value to 4.5, and be warming up to 70 ℃, keep 1.5h, reaction terminating.After the reaction system cooling, product is carried out magnetic separate, repeatedly with ethanol and distilled water washing, 40 ℃ of dried nanometer Fe to surperficial linoleic acid modification
3O
4
Embodiment 5
Method according to Sun prepares nano Co Fe
2O
4(Monodisperse MFe
2O
4(M=Fe, Co, Mn) Nanoparticles, J.Am.Chem.Soc.2004; 126,273), get 4g and pulverize, put into the there-necked flask of 2L; Add 1000mL distilled water, ultrasonic dispersing 4h is put in the water-bath and is warming up to 50 ℃ under the mechanical agitation; Drip 0.4mol/LNaOH solution and regulate pH value to 10, in solution, drip the 0.9g10-undecenoic acid again, keep 1h; Drip the hydrochloric acid solution of 0.4mol/L, regulate pH value to 4, and be warming up to 70 ℃, keep 1.5h, reaction terminating.After the reaction system cooling, product is carried out magnetic separate, repeatedly with ethanol and distilled water washing, 40 ℃ of dried nano Co Fe to surperficial 10 hendecenoic acid modification
2O
4
Method according to Sun prepares nanometer MnFe
2O
4(Monodisperse MFe2O4 (M=Fe, Co, Mn) Nanoparticles, J.Am.Chem.Soc.2004; 126,273), get 4g and pulverize, put into the there-necked flask of 2L; Add 1000mL distilled water, ultrasonic dispersing 4h is put in the water-bath and is warming up to 50 ℃ under the mechanical agitation; Drip 0.4mol/LNaOH solution and regulate pH value to 10, in solution, drip 1g oleic acid again, keep 1.5h; Drip the hydrochloric acid solution of 0.4mol/L, regulate pH value to 4, and be warming up to 70 ℃, keep 2h, reaction terminating.After the reaction system cooling, product is carried out magnetic separate, repeatedly with ethanol and distilled water washing, 40 ℃ of dried nanometer MnFe to surperficial oleic acid modification
2O
4
Embodiment 7
Fe with 19.8mL styrene, 6.6mL divinylbenzene, 21.1mL normal heptane, the mixing of 0.5g benzoyl peroxide and dissolving and the modification of 6.6g10-undecenoic acid
3O
4Together pour the 1000mL there-necked flask into, and be put in 80 ℃ of water-baths, mechanical agitation 15～30min, treat that solution has certain viscosity and mixes after, add the gelatin solution 240mL of 2wt%, stir down and be warming up to 80 ℃, maintenance 2h; Be warming up to 85 ℃, keep 2h; Be warming up to 90 ℃ again, keep 6h, the stopping of reaction.Reaction system cooling back discharging is cleaned with distilled water repeatedly, obtains magnetic resin after drying naturally.It is carried out sulfonation, obtain magnetic cation exchange resin catalyzer, specific saturation magnetization is 10.1, and acid capacity is 3.52, and particle diameter is 50～500 μ m.
Fe with 19.8mL styrene, 7.4mL divinylbenzene, 16.0mL isooctanol, 1.1g benzoyl peroxide mixing and stirring and the modification of 8g oleic acid
3O
4Together pour the 1000mL there-necked flask into, and be put in 80 ℃ of water-baths, mechanical agitation 15～30min, treat that solution has certain viscosity and mixes after, add the poly-vinyl alcohol solution 240mL of 4wt%, stir down and be warming up to 80 ℃, maintenance 2h; Be warming up to 85 ℃, keep 2h; Be warming up to 90 ℃ again, keep 6h, the stopping of reaction.Reaction system cooling back discharging is cleaned with distilled water repeatedly, obtains magnetic resin after drying naturally.It is carried out sulfonation, obtain magnetic cation exchange resin catalyzer, specific saturation magnetization is 11.5, and acid capacity is 4.08, and particle diameter is 50～500 μ m.
Embodiment 9
γ-Fe with 19.8mL styrene, 8.3mL divinylbenzene, 20.0mL neopentyl alcohol, 1.6g benzoyl peroxide mixing and stirring and the modification of 10g dodecylic acid
2O
3Together pour the 1000mL there-necked flask into, and be put in 80 ℃ of water-baths, mechanical agitation 15～30min, treat that solution has certain viscosity and mixes after, add the poly-vinyl alcohol solution 240mL of 4wt%, stir down and be warming up to 80 ℃, maintenance 2h; Be warming up to 85 ℃, keep 2h; Be warming up to 90 ℃ again, keep 6h, the stopping of reaction.Reaction system cooling back discharging is cleaned with distilled water repeatedly, obtains magnetic resin after drying naturally.It is carried out sulfonation, obtain magnetic cation exchange resin catalyzer, specific saturation magnetization is 13.1, and acid capacity is 4.26, and particle diameter is 50～500 μ m.
CoFe with 19.8mL styrene, 7.4mL divinylbenzene, 24.5mL normal heptane, 0.9g benzoyl peroxide mixing and stirring and the modification of 12g10-undecenoic acid
2O
4Together pour the 1000mL there-necked flask into, and be put in 80 ℃ of water-baths, mechanical agitation 15～30min, treat that solution has certain viscosity and mixes after, add the gelatin solution 240mL of 3wt%, stir down and be warming up to 80 ℃, maintenance 2h; Be warming up to 85 ℃, keep 2h; Be warming up to 90 ℃ again, keep 6h, the stopping of reaction.Reaction system cooling back discharging is cleaned with distilled water repeatedly, obtains magnetic resin after drying naturally.It is carried out sulfonation, obtain magnetic cation exchange resin catalyzer, specific saturation magnetization is 14.7, and acid capacity is 4.35, and particle diameter is 50～500 μ m.
Embodiment 11
MnFe with 19.8mL styrene, 7.4mL divinylbenzene, 18.0mL isoamyl alcohol, 1.5g benzoyl peroxide mixing and stirring and the modification of 5g oleic acid
2O
4Together pour the 1000mL there-necked flask into, and be put in 80 ℃ of water-baths, mechanical agitation 15～30min, treat that solution has certain viscosity and mixes after, add the poly-vinyl alcohol solution 240mL of 5wt%, stir down and be warming up to 80 ℃, maintenance 2h; Be warming up to 85 ℃, keep 2h; Be warming up to 90 ℃ again, keep 6h, the stopping of reaction.Reaction system cooling back discharging is cleaned with distilled water repeatedly, obtains magnetic resin after drying naturally.It is carried out sulfonation, obtain magnetic cation exchange resin catalyzer, specific saturation magnetization is 7.07, and acid capacity is 4.17, and particle diameter is 50～500 μ m.
Fe with 19.8mL styrene, 7mL divinylbenzene, 23.1mL normal heptane, the mixing of 1.3g benzoyl peroxide and dissolving and the modification of 11g linoleic acid
3O
4Together pour the 1000mL there-necked flask into, and be put in 80 ℃ of water-baths, mechanical agitation 15～30min, treat that solution has certain viscosity and mixes after, add the poly-vinyl alcohol solution 240mL of 4wt%, stir down and be warming up to 80 ℃, maintenance 2h; Be warming up to 85 ℃, keep 2h; Be warming up to 90 ℃ again, keep 6h, the stopping of reaction.Reaction system cooling back discharging is cleaned with distilled water repeatedly, obtains magnetic resin after drying naturally.It is carried out sulfonation, obtain magnetic cation exchange resin catalyzer, specific saturation magnetization is 13.4, and acid capacity is 4.24, and particle diameter is 50～500 μ m.
Claims (16)
1. the preparation method of a magnetic cation exchange resin catalyzer may further comprise the steps:
(1) in the water of pH value 9～12, nano level magnetic metal oxide is mixed with LCFA, regulate pH value to 4～5, obtain the nano magnetic particle of modification after the reaction, described LCFA is the carboxylic acid of C8～C24;
(2) with monomer, initator, crosslinking agent, pore-foaming agent with account for monomer and the modification magnetic particle of crosslinking agent gross weight 5～65% mixes, obtain magnetic resin after the polymerization, magnetic resin obtains final catalyst after sulfonating reaction.
2. according to the described method of claim 1; It is characterized in that; Mixed process in the step (1) is: nano level magnetic metal oxide is disperseed in water, regulate pH value to 9～12, under 40～55 ℃; The LCFA of adding and magnetic metal oxide mol ratio 0.1～0.6 continues reaction 1.5～3h.
3. according to the described method of claim 1, it is characterized in that the reaction condition in the step (1) is: be warming up to 55～75 ℃, reaction 1.5～3h.
4. according to the described method of claim 1, it is characterized in that the polymerization process in the step (2) comprises: behind 60～80 ℃ of pre-polymerization 5～40min, add dispersant, mode polymerization 6～14h that the employing stage heats up between 80 ℃ to 95 ℃.
5. according to the described method of claim 1, it is characterized in that said magnetic metal oxide is Fe
3O
4, γ-Fe
2O
3, CoFe
2O
4And MnFe
2O
4In one or more, its particle diameter is 3～50nm.
6. according to the described method of claim 5, it is characterized in that the particle diameter of magnetic metal oxide is 10～25nm.
7. according to the described method of claim 1, it is characterized in that the carbochain end of LCFA contains unsaturated double-bond.
8. according to the described method of claim 7, it is characterized in that LCFA is 10 hendecenoic acid, 11-lauroleic acid, 12-tridecylenic acid or 14-pentadecylenic acid.
9. according to the described method of claim 2, it is characterized in that in the step (1), the mol ratio of LCFA and magnetic metal oxide is 0.1～0.3.
10. according to the described method of claim 1, it is characterized in that the described monomer of step (2) is selected from one or more in the substituted styrene of styrene, alkyl or halogen atom.
11., it is characterized in that the described crosslinking agent of step (2) is divinylbenzene, di isopropenylbenzene, divinyl toluene or divinyl xylenes according to the described method of claim 1.
12., it is characterized in that the consumption of crosslinking agent is 4～40% of monomer and a crosslinking agent gross weight according to the described method of claim 11.
13., it is characterized in that the dispersant in the step (2) is the aqueous solution of water soluble polymer according to the described method of claim 4, the consumption of dispersant is monomer and crosslinking agent cumulative volume 1～10 times.
14., it is characterized in that water soluble polymer is selected from one or more in gelatin, starch, bassora gum, polyvinyl alcohol, polyacrylate, methylcellulose and the CMC according to the described method of claim 13.
15., it is characterized in that the pore-foaming agent described in the step (2) is alcohol, alkane, gasoline or Chinese wax according to the described method of claim 1.
16., it is characterized in that in the step (2), the consumption of pore-foaming agent is 30～50% of monomer, crosslinking agent and a pore-foaming agent gross weight according to the described method of claim 15.
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