CN100543052C - The preparation method of nano-level crosslinked polystyrene hollow microsphere - Google Patents
The preparation method of nano-level crosslinked polystyrene hollow microsphere Download PDFInfo
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- CN100543052C CN100543052C CNB2007101327044A CN200710132704A CN100543052C CN 100543052 C CN100543052 C CN 100543052C CN B2007101327044 A CNB2007101327044 A CN B2007101327044A CN 200710132704 A CN200710132704 A CN 200710132704A CN 100543052 C CN100543052 C CN 100543052C
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- 239000004793 Polystyrene Substances 0.000 title claims abstract description 11
- 239000004005 microsphere Substances 0.000 title claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- BANXPJUEBPWEOT-UHFFFAOYSA-N isohexadecane Natural products CCCCCCCCCCCCCC(C)C BANXPJUEBPWEOT-UHFFFAOYSA-N 0.000 claims abstract description 8
- KUVMKLCGXIYSNH-UHFFFAOYSA-N isopentadecane Natural products CCCCCCCCCCCCC(C)C KUVMKLCGXIYSNH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 10
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 238000002525 ultrasonication Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical group CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 28
- 239000012071 phase Substances 0.000 description 11
- 230000010355 oscillation Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
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- Polymerisation Methods In General (AREA)
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The preparation method of nano-level crosslinked polystyrene hollow microsphere, the invention is characterized in, at first emulsifying agent, assistant for emulsifying agent are added to the water, initiator is dissolved in the oil phase of vinylbenzene, Vinylstyrene and octane-iso or n-Hexadecane formation in addition, oil phase is added to the water ultrasonic emulsification, polymerization heats up under the mechanical stirring, react after 24 hours, centrifugation, vacuum-drying obtain Powdey cross-linked polystyrene hollow microsphere.
Description
(1) technical field:
The invention belongs to the polymer-function material technical field, be specifically related to a kind of preparation method with nano-level crosslinked polystyrene microballoon of hollow structure.
(2) technical background:
Polymer particle with hollow structure is the material that a class has special performance and extensive use.By the storage of cavity and the sustained release effect of shell, hollow-particle can be used as the carrier of catalyzer, medicine, biotechnological formulation and various specific functionality reagent, the effect of reach encapsulation, transport, constant speed being fixed a point slowly-releasing.Secondly, utilize special effectses such as its heat insulation, scattering that light, heat etc. are produced, hollow-particle can be used as insulation agent, organic white pigment, lightweight weighting agent etc. and is widely used in industries such as coating, papermaking, leather, makeup and building.Therefore, the research of polymkeric substance hollow-particle is subjected to extensive concern, and various preparation methods are also reported in succession.
Research about the preparation of hollow microsphere and structure control thereof is a lot, and the principle according to hollow forms roughly can be divided into following three major types: (1) utilize the polymeric contraction (reference 1:Hu etc., Biomaterials, 2002,23,3193-3201); (2) the utilization self-assembly effect of effect non-chemically (reference 2:Jo etc., European Polymer Journal, 1996,32,967-972); (3) utilize the template action of the material of various dissimilar, forms and states of matter for matrix.Wherein, template is a kind of both tradition, also modal method, and template used can be metal, inorganics, organic polymer material.As, it is template that people such as Yang Zhenglong adopt inorganic particulate, by introducing coupling agent earlier on its surface, form polymer layer through microemulsion polymerization method on the inorganic particulate surface then, make the composite particles of inorganic core/polymer shell, use the inorganic core of strong acid etching inside again, obtain the polymer particle (reference 3: Yang Zhenglong etc. of hollow structure at last, Chinese invention patent, application number 200410089039.1).People such as Donath repeat the polyelectrolyte of alternating deposit polyphenyl sodium sulfonate and two kinds of oppositely chargeds of polyacrylamide on crosslinked melamine resin mono-dispersion microballoon, form after the multilayer shell of certain intensity, erode template particles again, obtain hollow-particle (reference 4:Donath etc., Angew.Chem.Int.Ed., 1998,37,2201-2205).Obviously, these class methods often need to finish through multistep, and the removal of template further makes process complicated.Yet, as the preparation method of soft template the removal process of template is simplified relatively with fluent meterial.As, at a polystyrene seed particle, octane-iso, in the system that anionic surfactant and water-soluble alcohol (as methyl alcohol) are formed, carry out vinylbenzene and a small amount of acrylic acid letex polymerization earlier, along with monomeric consumption, between the polymkeric substance that is produced and hydrocarbon and monomeric mixed solution, occur being separated, and on the interface, formed low-molecular-weight polymer phase, add vinylbenzene and Vinylstyrene this moment again, make its polymerization form crosslinked shell, last, the octane-iso of removing particle inside by vacuum or air-flow obtains polymkeric substance hollow-particle (reference 5:McDonald etc., Macromolecules, 2000,33,1593-1605).Similarly study in addition with it, with monomer styrene and N, Phenhenzamine methacrylic ester and n-Hexadecane and oil-soluble initiator are mixed into oil phase, by the glassy membrane that has uniform micro it is dispersed in aqueous phase then and forms monomer droplet, make its polymerization form bigger micron order hollow microsphere (reference 6:Ma etc., Macromol.Symp., 2002 of particle diameter again, 179,223-240).
(3) summary of the invention:
The objective of the invention is to propose a kind of by in the mini-emulsion polymerization system, adopting soft template to prepare the method for nano-level crosslinked polystyrene hollow microsphere.
The process of method proposed by the invention is: monomer styrene and Vinylstyrene, hydrophobic organic compound and oil-soluble initiator join the aqueous phase that contains emulsifying agent and assistant for emulsifying agent after pre-mixing, pre-emulsification under ultrasonication, then under churned mechanically effect, improve temperature and allow its polymerization.The gained emulsion obtains the structure nano-level crosslinked polystyrene hollow microsphere different with the cavity rate after vacuum-drying.
Thought of the present invention and technological core are: (1) is in the mini-emulsion polymerization system, there is not polymeric hydrophobic organic compound simultaneously in monomer droplet inside, form between it and the polymer chain in the polymerization process and be separated, help cavity structure to form, played the effect of dynamic soft template; (2) existence of Vinylstyrene makes polymkeric substance form the derivatized polymers with sufficient intensity in diffusion and deposition; (3) mini-emulsion polymerization can so that to the particle diameter of hollow-particle be in the nano level scope; (4) can be by changing the consumption of hydrophobic organic compound, the cavity size and the structure of control particles such as monomer composition and temperature; (5) owing to the hydrophobic organic compound as soft template is volatile liquid state, the removal of template is integrated with the drying of separating of particle, process is simple.
Nano-level crosslinked polystyrene hollow microsphere proposed by the invention, its concrete steps are as follows:
1. pre-emulsification: take by weighing a certain amount of emulsifying agent and assistant for emulsifying agent, add and fill in the container of distilled water, sonic oscillation number minute in 45 ℃ water-bath makes its thorough mixing form uniform water.Other takes by weighing a certain amount of monomer styrene and Vinylstyrene, hydrophobic organic compound, adds the initiator benzoyl peroxide, with the pre-mixed aqueous phase of this oil phase input, continues in 45 ℃ of water-baths sonic oscillation number minute.
In above-mentioned system, Vinylstyrene accounts for the 20-90% of whole monomer weights;
In above-mentioned system, hydrophobic organic compound is octane-iso, n-Hexadecane etc., and its consumption is 0.25-2 a times of whole monomer weights;
In above-mentioned system, emulsifying agent is sodium lauryl sulphate, sodium laurylsulfonate and Sodium dodecylbenzene sulfonate etc., and its consumption is the 1.7-1.9% of monomer and octane-iso or n-Hexadecane gross weight; Assistant for emulsifying agent can adopt dodecane, and consumption is the 4.2-4.8% of monomer and octane-iso or n-Hexadecane gross weight;
In above-mentioned system, the consumption of initiator benzoyl peroxide is 2.5% of a total monomer weight.
2. synthetic: as gained system in the step 1 to be warming up to 60 ℃-85 ℃, to be about at rotating speed under 300 rev/mins the mechanical stirring, react after 24 hours, naturally cool to room temperature.
3. dry: as after centrifugation,, octane-iso or n-Hexadecane in the particle fully to be discharged step 2 gained emulsion, make powdered samples again through 60 ℃ of vacuum-dryings.
(4) embodiment:
Embodiment 1:
Take by weighing the sodium lauryl sulphate of 0.080g and the dodecane of 0.2g, add and to fill in the four neck flasks of 40g distilled water, in 45 ℃ water-bath sonic oscillation 5-10 minute, make sodium lauryl sulphate and dodecane thorough mixing form uniform water.Other takes by weighing the octane-iso of the Vinylstyrene of vinylbenzene, 0.7g of 1.3g and 2.6g and mixes, and with the benzoyl peroxide input of 0.05g wherein, makes uniform oil phase.This oil phase is dropped into above-mentioned aqueous phase, continued in 45 ℃ of water-baths sonic oscillation 5-10 minute.The gained system is transferred in 60 ℃ the water-bath, is about at rotating speed under 300 rev/mins the mechanical stirring, be warming up to 70 ℃ gradually, react after 24 hours, naturally cool to room temperature.After centrifugation,, the octane-iso in the particle is fully discharged the gained emulsion, make powdered samples again through 60 ℃ of vacuum-dryings.
Observation post gets particle and has hollow structure under transmission electron microscope, and particle size range is 300-700nm.
Embodiment 2:
Take by weighing the sodium lauryl sulphate of 0.067g and the dodecane of 0.17g, add and to fill in the four neck flasks of 40g distilled water, in 45 ℃ water-bath sonic oscillation 5-10 minute, make sodium lauryl sulphate and dodecane thorough mixing form uniform water.Other takes by weighing the octane-iso of the Vinylstyrene of vinylbenzene, 0.7g of 1.3g and 1.7g and mixes, and with the benzoyl peroxide input of 0.05g wherein, makes uniform oil phase.This oil phase is dropped into above-mentioned aqueous phase, continued in 45 ℃ of water-baths sonic oscillation 5-10 minute.The gained system is transferred in 60 ℃ the water-bath, is about at rotating speed under 300 rev/mins the mechanical stirring, be warming up to 70 ℃ gradually, react after 24 hours, naturally cool to room temperature.After centrifugation,, the octane-iso in the particle is fully discharged the gained emulsion, make powdered samples again through 60 ℃ of vacuum-dryings.
Observation post gets particle and has hollow structure under transmission electron microscope, and particle size range is 300-700nm.
Embodiment 3:
Take by weighing the sodium lauryl sulphate of 0.067g and the dodecane of 0.17g, add and to fill in the four neck flasks of 40g distilled water, in 45 ℃ water-bath sonic oscillation 5-10 minute, make sodium lauryl sulphate and dodecane thorough mixing form uniform water.Other takes by weighing the octane-iso of the Vinylstyrene of vinylbenzene, 1.11g of 0.89g and 1.7g and mixes, and with the benzoyl peroxide input of 0.05g wherein, makes uniform oil phase.This oil phase is dropped into above-mentioned aqueous phase, continued in 45 ℃ of water-baths sonic oscillation 5-10 minute.The gained system is transferred in 60 ℃ the water-bath, is about at rotating speed under 300 rev/mins the mechanical stirring, be warming up to 70 ℃ gradually, react after 24 hours, naturally cool to room temperature.After centrifugation,, the octane-iso in the particle is fully discharged the gained emulsion, make powdered samples again through 60 ℃ of vacuum-dryings.
Observation post gets particle and has hollow structure under transmission electron microscope, and particle size range is 500-800nm.
Embodiment 4:
Take by weighing the sodium lauryl sulphate of 0.072g and the dodecane of 0.18g, add and to fill in the four neck flasks of 40g distilled water, in 45 ℃ water-bath sonic oscillation 5-10 minute, make sodium lauryl sulphate and dodecane thorough mixing form uniform water.Other takes by weighing the octane-iso of the Vinylstyrene of vinylbenzene, 1.84g of 0.16g and 2.0g and mixes, and with the benzoyl peroxide input of 0.05g wherein, makes uniform oil phase.This oil phase is dropped into above-mentioned aqueous phase, continued in 45 ℃ of water-baths sonic oscillation 5-10 minute.The gained system is transferred in 60 ℃ the water-bath, is about at rotating speed under 300 rev/mins the mechanical stirring, be warming up to 70 ℃ gradually, react after 24 hours, naturally cool to room temperature.After centrifugation,, the octane-iso in the particle is fully discharged the gained emulsion, make powdered samples again through 60 ℃ of vacuum-dryings.
Observation post gets particle and has hollow structure under transmission electron microscope, and particle size range is 400-600nm.
Claims (1)
1. the preparation method of a nano-level crosslinked polystyrene hollow microsphere, it is characterized in that, at first emulsifying agent and assistant for emulsifying agent are added to the water, in addition initiator is dissolved in the oil phase of vinylbenzene, Vinylstyrene and octane-iso or n-Hexadecane formation, oil phase is added to the water, under 45 ℃ and ultrasonication, carry out pre-emulsification, with this emulsion under mechanical agitation, the intensification polymerization, reacted 24 hours, and, obtained Powdered nano-level crosslinked polystyrene hollow microsphere through centrifugation, vacuum-drying; Vinylstyrene accounts for the 20-90% of whole monomer weights, the consumption of octane-iso or n-Hexadecane is 0.25-2 a times of whole monomer weights, emulsifying agent is a kind of in sodium lauryl sulphate, sodium laurylsulfonate and the Sodium dodecylbenzene sulfonate, its consumption is the 1.7-1.9% of monomer and octane-iso or n-Hexadecane gross weight, assistant for emulsifying agent is a dodecane, its consumption is the 4.2-4.8% of monomer and octane-iso or n-Hexadecane gross weight, initiator is a benzoyl peroxide, and its consumption is 2.5% of a total monomer weight.
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| CN102268141B (en) * | 2011-05-18 | 2012-10-03 | 中国科学院长春应用化学研究所 | Method for preparing hollow porous material |
| CN103421253B (en) * | 2012-05-17 | 2016-07-06 | 中国石油化工股份有限公司 | The preparation method of polystyrene hollow microsphere and application thereof |
| CN104031197A (en) * | 2014-02-11 | 2014-09-10 | 华南理工大学 | Hollow polymer emulsion particle and preparation method |
| CN104673004B (en) * | 2015-03-22 | 2016-10-12 | 河北工业大学 | A kind of organic high molecular polymer super hydrophobic coating and application thereof |
| CN105440196B (en) * | 2015-12-30 | 2018-11-06 | 武汉工程大学 | A kind of polystyrene-acrylate copolymer microballoon and preparation method thereof |
| CN105733392B (en) * | 2016-03-11 | 2017-11-10 | 大连理工大学 | Submicron order polydivinylbenezene particle and its coating production with high temperature resistant and super-hydrophobicity |
| CN107868161B (en) * | 2017-12-07 | 2020-06-05 | 张振 | Preparation method and application of polymer hollow microcapsule |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN108641032B (en) * | 2018-04-10 | 2020-06-26 | 常州大学 | Method for preparing nano hollow reactor by inverse miniemulsion polymerization |
| CN109627385B (en) * | 2018-12-12 | 2021-04-09 | 合众（佛山）化工有限公司 | Polystyrene microsphere modified acrylic waterborne resin and preparation method thereof |
| CN109864967B (en) * | 2019-03-04 | 2021-09-14 | 金陵科技学院 | temperature/pH responsive carboxylated nano hydrogel and preparation method thereof |
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| CN1805192A (en) * | 2005-01-10 | 2006-07-19 | 比亚迪股份有限公司 | Preparation method of electro-catalyst for fuel cells |
| CN1803869A (en) * | 2005-12-21 | 2006-07-19 | 南开大学 | Preparation method of polar group-containing absorptive resin and application thereof in preparation of high-purity sanguinarin |
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| CN1805192A (en) * | 2005-01-10 | 2006-07-19 | 比亚迪股份有限公司 | Preparation method of electro-catalyst for fuel cells |
| CN1803869A (en) * | 2005-12-21 | 2006-07-19 | 南开大学 | Preparation method of polar group-containing absorptive resin and application thereof in preparation of high-purity sanguinarin |
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