CN102408520B - Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere - Google Patents
Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere Download PDFInfo
- Publication number
- CN102408520B CN102408520B CN201110284936.8A CN201110284936A CN102408520B CN 102408520 B CN102408520 B CN 102408520B CN 201110284936 A CN201110284936 A CN 201110284936A CN 102408520 B CN102408520 B CN 102408520B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- preparation
- monodisperse
- monomer
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000004044 response Effects 0.000 title abstract description 6
- 230000005389 magnetism Effects 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 230000004043 responsiveness Effects 0.000 claims abstract description 28
- 239000011258 core-shell material Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000007885 magnetic separation Methods 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 10
- 239000011324 bead Substances 0.000 abstract description 7
- 229910000859 α-Fe Inorganic materials 0.000 abstract description 6
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 238000012673 precipitation polymerization Methods 0.000 abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- -1 ethylene glycol dimethacrylic acid ester Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- RDBKQHSHFRJGAT-UHFFFAOYSA-N C(CO)O.CC(=CC(=O)O)C Chemical compound C(CO)O.CC(=CC(=O)O)C RDBKQHSHFRJGAT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
本发明涉及一种纳米级单分散高磁响应性核壳磁性聚合物微球的制备方法，用于解决现有的制备方法所制备的单分散铁酸盐纳米磁珠磁响应性低的技术问题。技术方案是以溶剂热法制备的单分散高磁响应性Fe3O4为核，丙烯酸类单体作为功能单体，通过沉淀聚合法制备了一种表面含羧基的单分散高磁响应性和高磁含量的纳米级高交联度核壳磁性聚合物微球。与传统的磁球制备方法相比，该法制备的磁球在单分散性和磁响应性方面都得到了较大的提高，磁响应性提高到68.4～80.1emu/g。只需选择合适的交联剂和丙烯酸类单体的用量，经常规沉淀聚合反应，既可得到预先设定的粒径的单分散磁性聚合物微球。
The invention relates to a preparation method of nano-scale monodisperse high magnetic response core-shell magnetic polymer microspheres, which is used to solve the technical problem of low magnetic response of monodisperse ferrite nano magnetic beads prepared by the existing preparation method . The technical solution is to use the monodisperse high magnetic responsiveness Fe 3 O 4 prepared by the solvothermal method as the core, and the acrylic monomer as the functional monomer. Nanoscale highly cross-linked core-shell magnetic polymer microspheres with high magnetic content. Compared with the traditional method of preparing magnetic spheres, the magnetic spheres prepared by this method have been greatly improved in terms of monodispersity and magnetic responsiveness, and the magnetic responsiveness has increased to 68.4-80.1emu/g. Only need to select the appropriate amount of crosslinking agent and acrylic monomer, through conventional precipitation polymerization, can obtain the pre-set particle size monodisperse magnetic polymer microspheres.
Description
技术领域 technical field
本发明涉及一种磁性聚合物微球的制备方法，特别是涉及一种纳米级单分散高磁响应性核壳磁性聚合物微球的制备方法。The invention relates to a preparation method of magnetic polymer microspheres, in particular to a preparation method of nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic response.
背景技术 Background technique
磁性高分子微球由于同时具有无机磁性物质的磁响应性和有机高分子的表面功能性(如-COOH、-OH、-NH2、-SH等)，在外加磁场下能方便、快速、高效地从介质分离，因此它在医学、分子生物学、生物化学等领域具有广泛的应用前景。Because magnetic polymer microspheres have both the magnetic responsiveness of inorganic magnetic substances and the surface functionality of organic polymers (such as -COOH, -OH, -NH 2 , -SH, etc.), they can be conveniently, quickly and efficiently Therefore, it has broad application prospects in medicine, molecular biology, biochemistry and other fields.
目前，磁性高分子复合微球的制备方法主要有无皂乳液聚合、细乳液聚合、分散聚合、悬浮聚合、反相微乳液聚合等。但是乳液聚合通常得到单分散的亚微米级球状粒子，悬浮聚合虽然可以得到微米级球状粒子，然而粒径分布较宽。此外，以上方法得到的磁性微球的磁含量和磁响应性都较低，且需用适当的表面活性剂。At present, the preparation methods of magnetic polymer composite microspheres mainly include soap-free emulsion polymerization, miniemulsion polymerization, dispersion polymerization, suspension polymerization, and inverse microemulsion polymerization. However, emulsion polymerization usually obtains monodisperse submicron-sized spherical particles, while suspension polymerization can obtain micron-sized spherical particles, but the particle size distribution is relatively wide. In addition, the magnetic content and magnetic responsiveness of the magnetic microspheres obtained by the above method are low, and appropriate surfactants are required.
文献“公开号是CN1645530的中国发明专利”公开了一种合成系列单分散铁酸盐纳米磁珠的方法。该方法以可溶性三价铁离子盐为原料，在乙二醇溶液中，于200～300℃下进行溶剂热反应，形成Fe3O4纳米磁珠。在相同的反应条件下，通过添加一种或多种二价可溶性金属离子的盐与可溶性三价铁离子盐共同进行反应，控制添加量，使二价金属离子与三价铁离子的摩尔比为0.01～1∶2，形成铁氧体纳米磁珠及复合铁氧体纳米磁珠。但是该方法制备的单分散铁酸盐纳米磁珠存在的缺点是磁响应性低。The document "Chinese Invention Patent Publication No. CN1645530" discloses a method for synthesizing a series of monodisperse ferrite nano-magnetic beads. In the method, soluble ferric ion salt is used as a raw material, and a solvothermal reaction is carried out in an ethylene glycol solution at 200-300° C. to form Fe3O4 nanometer magnetic beads. Under the same reaction conditions, by adding one or more salts of divalent soluble metal ions and soluble ferric ion salts to react together, the amount of addition is controlled so that the molar ratio of divalent metal ions to ferric ions is 0.01～1:2 to form ferrite nano magnetic beads and composite ferrite nano magnetic beads. However, the monodisperse ferrite nano-magnetic beads prepared by this method have the disadvantage of low magnetic response.
发明内容 Contents of the invention
为了克服现有的制备方法所制备的单分散铁酸盐纳米磁珠磁响应性低的不足，本发明提供一种纳米级单分散高磁响应性核壳磁性聚合物微球的制备方法。该方法以溶剂热法制备的单分散高磁响应性Fe3O4为核，以丙烯酸类单体作为功能性单体，通过沉淀聚合法制备了高磁响应性和高磁含量且表面含羧基的纳米级单分散高交联度核壳磁性聚合物微球。In order to overcome the deficiency of low magnetic responsiveness of monodisperse ferrite nano magnetic beads prepared by the existing preparation method, the present invention provides a preparation method of nanoscale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness. In this method, monodisperse highly magnetically responsive Fe3O4 prepared by solvothermal method is used as the core, and acrylic monomers are used as functional monomers to prepare high magnetic responsiveness and high magnetic content with carboxyl groups on the surface Nanoscale monodisperse highly cross-linked core-shell magnetic polymer microspheres.
本发明解决其技术问题所采用的技术方案是：一种纳米级单分散高磁响应性核壳磁性聚合物微球的制备方法，其特点是包括以下步骤：The technical solution adopted by the present invention to solve the technical problem is: a preparation method of nano-scale monodisperse highly magnetic responsive core-shell magnetic polymer microspheres, which is characterized in that it comprises the following steps:
(1)在配有冷凝管的反应器中，加入85～100wt％的乙腈和0～15wt％的醇；(1) in the reactor that is equipped with condenser, add the acetonitrile of 85～100wt% and the alcohol of 0～15wt%;
(2)将相对单体混合液3～17wt％的Fe3O4微球加入到装有乙腈和醇的上述反应器中；(2) Fe 3 O 4 microspheres of 3 to 17 wt% relative to the monomer mixture are added to the above-mentioned reactor equipped with acetonitrile and alcohol;
(3)称取50～100wt％的交联剂单体和0～50wt％丙烯酸类单体组成的单体混合液，以及单体混合液0.1～5wt％的引发剂，振荡溶解后，加入到上述反应器中，混合均匀；(3) Weigh the monomer mixed solution composed of 50-100wt% cross-linking agent monomer and 0-50wt% acrylic monomer, and 0.1-5wt% initiator of the monomer mixed solution, shake and dissolve, add to In the above reactor, mix evenly;
(4)将上述反应器逐步升温至65～85℃，聚合8～20h；(4) Gradually raise the temperature of the above-mentioned reactor to 65-85°C, and polymerize for 8-20 hours;
(5)将步骤(4)得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到表面含羧基的纳米级单分散高磁响应性核壳磁性聚合物微球。(5) Carry out magnetic separation on the product obtained in step (4), pour off the supernatant liquid, add absolute ethanol to disperse by ultrasonic, and then carry out magnetic separation; repeat washing several times in this way to remove redundant monomers and polymers. Vacuum drying at room temperature can obtain nano-scale monodisperse core-shell magnetic polymer microspheres with carboxyl groups on the surface and high magnetic responsiveness.
本发明的有益效果是：由于以溶剂热法制备的单分散高磁响应性Fe3O4为核，丙烯酸类单体作为功能单体，通过沉淀聚合法制备了一种表面含羧基的单分散高磁响应性和高磁含量的纳米级高交联度核壳磁性聚合物微球。与传统的磁球制备方法相比，该法制备的磁球在单分散性和磁响应性方面都得到了较大的提高，磁响应性提高到68.4～80.1emu/g。只需选择合适的交联剂和丙烯酸类单体的用量，经常规沉淀聚合反应，既可得到预先设定的粒径的单分散磁性聚合物微球。同时，由于功能单体中具有反应性的羧基基团，可以满足生物工程及分离工程等诸多领域对不同粒径的纳米级单分散核壳磁性微球的需求。The beneficial effects of the present invention are: since the monodisperse high magnetic response Fe 3 O 4 prepared by the solvothermal method is used as the core, and the acrylic monomer is used as the functional monomer, a monodisperse carboxyl group-containing surface is prepared by precipitation polymerization. Nanoscale highly cross-linked core-shell magnetic polymer microspheres with high magnetic responsiveness and high magnetic content. Compared with the traditional method of preparing magnetic spheres, the magnetic spheres prepared by this method have been greatly improved in terms of monodispersity and magnetic responsiveness, and the magnetic responsiveness has increased to 68.4-80.1emu/g. Only need to select the appropriate amount of crosslinking agent and acrylic monomer, through conventional precipitation polymerization, can obtain the pre-set particle size monodisperse magnetic polymer microspheres. At the same time, due to the reactive carboxyl group in the functional monomer, it can meet the needs of nano-scale monodisperse core-shell magnetic microspheres with different particle sizes in many fields such as bioengineering and separation engineering.
下面结合附图和实施例对本发明作详细说明。The present invention will be described in detail below in conjunction with the accompanying drawings and embodiments.
附图说明 Description of drawings
图1是实施例3制备的纳米级单分散高磁响应性核壳磁性聚合物微球的TEM照片。Fig. 1 is the TEM photo of the nanoscale monodisperse high magnetic responsive core-shell magnetic polymer microspheres prepared in Example 3.
图2是实施例6制备的纳米级单分散高磁响应性核壳磁性聚合物微球的TEM照片。Figure 2 is a TEM photo of the nanoscale monodisperse highly magnetically responsive core-shell magnetic polymer microspheres prepared in Example 6.
具体实施方式 Detailed ways
实施例1：在配有冷凝管的100mL反应器中，加入68g乙腈和12g甲醇；将0.012g Fe3O4微球加入到100mL反应器中；将0.13g EGDMA(乙二醇二甲基丙烯酸酯)和0.02g MAA(甲基丙烯酸)组成的单体混合液及0.001g的AIBN(偶氮二异丁腈)，振荡溶解后，加入到反应器中，混合均匀；逐步升温至65℃，聚合14h；将得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到深咖啡色的纳米级单分散高磁响应性核壳磁性聚合物微球。Embodiment 1: in the 100mL reactor that is equipped with condenser, add 68g acetonitrile and 12g methyl alcohol; 0.012g Fe 3 O 4 Microspheres are joined in the 100mL reactor; 0.13g EGDMA (ethylene glycol dimethacrylic acid ester) and 0.02g MAA (methacrylic acid) monomer mixture and 0.001g AIBN (azobisisobutyronitrile), after shaking and dissolving, add to the reactor and mix well; gradually raise the temperature to 65°C, Polymerize for 14 hours; perform magnetic separation on the obtained product, pour off the supernatant, add absolute ethanol for ultrasonic dispersion, and then perform magnetic separation; repeat this process for several times to remove excess monomer and polymer. After vacuum drying at room temperature, dark brown nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness are obtained.
经测试，所得到的纳米级单分散高磁响应性核壳磁性聚合物微球粒径为480nm，磁响应性为80.1emu/g，磁含量为94.8wt％。After testing, the obtained nano-scale monodisperse highly magnetic responsive core-shell magnetic polymer microsphere has a particle diameter of 480nm, a magnetic responsiveness of 80.1emu/g, and a magnetic content of 94.8wt%.
实施例2：在配有冷凝管的100mL反应器中，加入65g乙腈和8g正丁醇；将0.028g Fe3O4微球加入到100mL反应器中；将0.25g EGDMA(乙二醇二甲基丙烯酸酯)和0.14g AA(丙烯酸)组成的单体混合液及0.003g的BPO(过氧化二苯甲酰)，振荡溶解后，加入到反应器中，混合均匀；逐步升温至80℃，聚合10h；将得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到深咖啡色的纳米级单分散高磁响应性核壳磁性聚合物微球。Embodiment 2: in the 100mL reactor that is equipped with condenser tube, add 65g acetonitrile and 8g n-butanol; 0.028g Fe 3 O 4 Microspheres are joined in the 100mL reactor; 0.25g EGDMA (ethylene glycol dimethyl Acrylic acid ester) and 0.14g AA (acrylic acid) monomer mixture and 0.003g of BPO (dibenzoyl peroxide), after shaking and dissolving, add to the reactor, mix well; gradually heat up to 80 ° C, Polymerize for 10 hours; perform magnetic separation on the obtained product, pour off the supernatant, add absolute ethanol for ultrasonic dispersion, and then perform magnetic separation; repeat this process several times to remove excess monomer and polymer. After vacuum drying at room temperature, dark brown nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness are obtained.
经测试，所得到的纳米级单分散高磁响应性核壳磁性聚合物微球粒径为495nm，磁响应性为76.8emu/g，磁含量为93.5wt％。After testing, the obtained nano-scale monodisperse highly magnetic responsive core-shell magnetic polymer microsphere has a particle diameter of 495nm, a magnetic responsiveness of 76.8emu/g, and a magnetic content of 93.5wt%.
实施例3：在配有冷凝管的100mL反应器中，加入75g乙腈和5g异丙醇；将0.034g Fe3O4微球加入到100mL反应器中；将0.39g DVB(二乙烯基苯)和0.22gMAA(甲基丙烯酸)组成的单体混合液及0.009g的AIBN(偶氮二异丁腈)，振荡溶解后，加入到反应器中，混合均匀；逐步升温至84℃，聚合8h；将得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到深咖啡色的纳米级单分散高磁响应性核壳磁性聚合物微球。Example 3: In a 100mL reactor equipped with a condenser, add 75g acetonitrile and 5g isopropanol; 0.034g Fe 3 O Microspheres are added to a 100mL reactor; 0.39g DVB (divinylbenzene) and 0.22g of MAA (methacrylic acid) monomer mixture and 0.009g of AIBN (azobisisobutyronitrile), after shaking and dissolving, add to the reactor and mix well; gradually raise the temperature to 84°C, and polymerize for 8h; The obtained product is subjected to magnetic separation, the supernatant liquid is poured off, and anhydrous ethanol is added for ultrasonic dispersion, and then magnetic separation is carried out; repeated washing in this way is repeated several times to remove redundant monomers and polymers. After vacuum drying at room temperature, dark brown nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness are obtained.
经测试，所得到的纳米级单分散高磁响应性核壳磁性聚合物微球粒径为539nm，磁响应性为75.5emu/g，磁含量为92.1wt％。After testing, the obtained nano-scale monodisperse highly magnetic responsive core-shell magnetic polymer microsphere has a particle diameter of 539nm, a magnetic responsiveness of 75.5emu/g, and a magnetic content of 92.1wt%.
实施例4：在配有冷凝管的150mL反应器中，加入79g乙腈和12g乙醇；将0.071g Fe3O4微球加入到150mL反应器中；将0.58g EGDMA(乙二醇二甲基丙烯酸酯)和0.41g MAA(甲基丙烯酸)组成的单体混合液及0.014g的BPO(过氧化二苯甲酰)，振荡溶解后，加入到反应器中，混合均匀；逐步升温至79℃，聚合20h；将得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到深咖啡色的纳米级单分散高磁响应性核壳磁性聚合物微球。Embodiment 4: In the 150mL reactor that is equipped with condenser, add 79g acetonitrile and 12g ethanol; 0.071g Fe 3 O Microspheres are joined in 150mL reactor; 0.58g EGDMA (ethylene glycol dimethacrylic acid Ester) and 0.41g MAA (methacrylic acid) monomer mixture and 0.014g of BPO (dibenzoyl peroxide), after shaking and dissolving, add to the reactor and mix well; gradually heat up to 79 ° C, Polymerize for 20 hours; perform magnetic separation on the obtained product, pour off the supernatant, add absolute ethanol for ultrasonic dispersion, and then perform magnetic separation; repeat this process several times to remove redundant monomers and polymers. After vacuum drying at room temperature, dark brown nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness are obtained.
经测试，所得到的纳米级单分散高磁响应性核壳磁性聚合物微球粒径为574nm，磁响应性为73.8emu/g，磁含量为91.1wt％。After testing, the obtained nano-scale monodisperse highly magnetic responsive core-shell magnetic polymer microspheres have a particle diameter of 574nm, a magnetic responsiveness of 73.8emu/g, and a magnetic content of 91.1wt%.
实施例5：在配有冷凝管的150mL反应器中，加入90g乙腈和10g正丙醇(或异丁醇)；将0.085g Fe3O4微球加入到150mL反应器中；将0.68g DVB(二乙烯基苯)和0.51g AA(丙烯酸)组成的单体混合液及0.018g的BPO(过氧化二苯甲酰)，振荡溶解后，加入到反应器中，混合均匀；逐步升温至85℃，聚合15h；将得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到深咖啡色的纳米级单分散高磁响应性核壳磁性聚合物微球。Example 5: In a 150mL reactor equipped with a condenser, 90g of acetonitrile and 10g of n-propanol (or isobutanol) were added; 0.085g of Fe 3 O 4 microspheres were added to the 150mL reactor; 0.68g of DVB (divinylbenzene) and 0.51g AA (acrylic acid) monomer mixture and 0.018g of BPO (dibenzoyl peroxide), after shaking and dissolving, add in the reactor, mix well; gradually heat up to 85 ℃, polymerized for 15 hours; magnetically separated the obtained product, poured off the supernatant, added absolute ethanol for ultrasonic dispersion, and then carried out magnetic separation; repeated washing in this way several times to remove excess monomer and polymer. After vacuum drying at room temperature, dark brown nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness are obtained.
经测试，所得到的纳米级单分散高磁响应性核壳磁性聚合物微球粒径为591nm，磁响应性为72.9emu/g，磁含量为89.4wt％。After testing, the obtained nano-scale monodisperse core-shell magnetic polymer microsphere with high magnetic responsiveness has a particle diameter of 591nm, a magnetic responsiveness of 72.9emu/g, and a magnetic content of 89.4wt%.
实施例6：在配有冷凝管的150mL反应器中，加入110g乙腈；将0.15g Fe3O4微球加入到150mL反应器中；将1.0g DVB(二乙烯基苯)和1.0g MAA(甲基丙烯酸)组成的单体混合液及0.021g的AIBN(偶氮二异丁腈)，振荡溶解后，加入到反应器中，混合均匀；逐步升温至65℃，聚合18h；将得到的产物进行磁分离，倾去上层液，加入无水乙醇经超声分散，然后再进行磁分离；如此反复洗涤几次，以除去多余的单体和聚合物。在室温下真空干燥，即得到深咖啡色的纳米级单分散高磁响应性核壳磁性聚合物微球。Embodiment 6: in the 150mL reactor that is equipped with condenser, add 110g acetonitrile; 0.15g Fe 3 O 4 microspheres are joined in the 150mL reactor; 1.0g DVB (divinylbenzene) and 1.0g MAA ( Methacrylic acid) monomer mixture and 0.021g of AIBN (azobisisobutyronitrile), after shaking and dissolving, add to the reactor and mix evenly; gradually raise the temperature to 65°C, and polymerize for 18h; the obtained product Carry out magnetic separation, pour off the supernatant liquid, add absolute ethanol to disperse by ultrasonic, and then carry out magnetic separation; repeat the washing several times in this way to remove excess monomer and polymer. After vacuum drying at room temperature, dark brown nano-scale monodisperse core-shell magnetic polymer microspheres with high magnetic responsiveness are obtained.
经测试，所得到的纳米级单分散高磁响应性核壳磁性聚合物微球粒径为630nm，磁响应性为68.4emu/g，磁含量为86.1wt％。After testing, the obtained nano-scale monodisperse core-shell magnetic polymer microsphere with high magnetic responsiveness has a particle diameter of 630nm, a magnetic responsiveness of 68.4emu/g, and a magnetic content of 86.1wt%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110284936.8A CN102408520B (en) | 2011-09-22 | 2011-09-22 | Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110284936.8A CN102408520B (en) | 2011-09-22 | 2011-09-22 | Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408520A CN102408520A (en) | 2012-04-11 |
| CN102408520B true CN102408520B (en) | 2014-02-05 |
Family
ID=45910901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110284936.8A Active CN102408520B (en) | 2011-09-22 | 2011-09-22 | Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408520B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250327A (en) * | 2013-06-28 | 2014-12-31 | 中国科学院大连化学物理研究所 | Method for preparing particle size-controllable high-crosslinked monodispersed polydivinylbenzene microspheres |
| CN106117402B (en) * | 2016-07-04 | 2017-11-28 | 中北大学 | High-performance magnetorheological nano composite polymeric gel process for preparing |
| CN109939621B (en) * | 2019-03-08 | 2020-08-11 | 清华大学 | Method for preparing single-particle uniform coating shell layer by liquid phase interface crossing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645530A (en) * | 2004-11-12 | 2005-07-27 | 清华大学 | Method for synthesizing series single-dispersed ferrite nanometer magnetic beads |
| CN101549270A (en) * | 2009-04-03 | 2009-10-07 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
| CN101608020A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院理化技术研究所 | Magnetic Fe prepared by hydrothermal method3O4Polymer submicron sphere and application |
-
2011
- 2011-09-22 CN CN201110284936.8A patent/CN102408520B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1645530A (en) * | 2004-11-12 | 2005-07-27 | 清华大学 | Method for synthesizing series single-dispersed ferrite nanometer magnetic beads |
| CN101608020A (en) * | 2008-06-20 | 2009-12-23 | 中国科学院理化技术研究所 | Magnetic Fe prepared by hydrothermal method3O4Polymer submicron sphere and application |
| CN101549270A (en) * | 2009-04-03 | 2009-10-07 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408520A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Hydrophilic dual‐responsive magnetite/PMAA core/shell microspheres with high magnetic susceptibility and ph sensitivity via distillation‐precipitation polymerization | |
| CN100443508C (en) | Preparation method of functional polymer composite microspheres with fast magnetic field responsiveness | |
| CN101948554A (en) | Weak acid cation exchange microballoon resin of magnetic acrylic acid series and synthesis method thereof | |
| CN104761691B (en) | Have preparation method and obtained polymer microballoon and the application of granular gradient performance polymer microballoon | |
| CN101220187A (en) | A magnetic composite microsphere with core-shell structure and preparation method thereof | |
| CN102500290A (en) | Preparation method of monodisperse core-shell P(GMA-DVB)/Fe3O4 microspheres with high degree of crosslinking | |
| CN102174144B (en) | Fluorescent latex particles and preparation method thereof | |
| CN102417567B (en) | Preparation method for one-dimensional magnetic thermo-sensitivity nanochain | |
| CN103242494A (en) | Preparation method of composite microgel with temperature, pH and magnetic field sensitivities | |
| CN105131309B (en) | Nano combined latex particle dispersion liquid of lithium metasilicate magnesium of polymer/artificial synthesized and preparation method thereof | |
| CN112592423B (en) | Monodisperse Magnetic Microspheres | |
| CN103833942A (en) | Preparation method and use of diethylstibestrol molecularly-imprinted magnetic microspheres | |
| CN102408520B (en) | Preparation method for nano monodisperse high magnetism response nuclear shell magnetic polymer microsphere | |
| CN102786634B (en) | Preparation method of monodisperse surface-folded PMMA (polymethyl methacrylate) microsphere | |
| CN101838426B (en) | Synthesis method of superparamagnetic polymer microspheres | |
| CN102502873B (en) | Preparation method for one-dimensional magnetic nanochain | |
| CN116041745A (en) | A kind of surface epoxy functionalized magnetic polystyrene microsphere and its preparation method | |
| CN101544730A (en) | Method for preparing nanometer spherical polyelectrolyte brush with magnetic kernel | |
| CN103406108A (en) | Preparation method of carbon-based magnetic temperature-sensitive surface imprinted adsorbent | |
| CN115710373A (en) | Preparation method of hydrogel magnetic microspheres | |
| CN104031210B (en) | The preparation method of the monodisperse polystyrene microsphere emulsion of quaternary ammonium salt surface modification | |
| Liu et al. | A novel CoFe2O4/polyacrylate nanocomposite prepared via an in situ polymerization in emulsion system | |
| CN115975252B (en) | A method for preparing magnetic polymer microspheres with a double-layer shell structure | |
| CN103204967A (en) | Preparation of monodispersed magnetic fluorescent core-shell nano-microspheres | |
| CN103435740B (en) | A kind of manufacture method of water-soluble polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |