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Publication numberCN103632798 B
Publication typeGrant
Application numberCN 201310636021
Publication date24 Feb 2016
Filing date3 Dec 2013
Priority date3 Dec 2013
Also published asCN103632798A
Publication number201310636021.8, CN 103632798 B, CN 103632798B, CN 201310636021, CN-B-103632798, CN103632798 B, CN103632798B, CN201310636021, CN201310636021.8
Inventors乐长高, 谢宇, 潘建飞, 谢宗波, 黄彦, 李凤, 刘福明
Applicant东华理工大学, 南昌航空大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
一种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体的制备方法 A process for preparing 3-methyl-thiophene-coated nano nickel zinc ferrite magnetic particles in a liquid poly translated from Chinese
CN 103632798 B
Abstract  translated from Chinese
本发明公开了一种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体的制备方法,通过表面原位合成法将镍锌铁氧体粒子用聚3-甲基噻吩包覆,达到聚3-甲基噻吩牢固包裹镍锌铁氧体纳米颗粒的效果,具体采用共沉淀法先制备镍锌铁氧体纳米颗粒,随后用所制得镍锌铁氧体纳米颗粒制备镍锌铁氧体离子型磁性液体,再在镍锌铁氧体离子型磁性液体中加入3-甲基噻吩单体和引发剂原位聚合得到聚3-甲基噻吩良好包覆纳米镍锌铁氧体磁性粒子,最后用镍锌铁氧体/聚3-甲基噻吩复合颗粒制备出聚3-甲基噻吩包覆纳米镍锌铁氧体磁性粒子磁性液体。 The present invention discloses a poly-3-methylthiophene-coated nano-nickel-zinc ferrite particles of magnetic fluid preparation, through the surface in situ synthesis of nickel zinc ferrite particles were coated with poly 3-methylthiophene, to achieve the effect of poly 3-methylthiophene securely wrapped in nickel zinc ferrite nanoparticles to specific nickel zinc ferrite nanoparticles prepared by co-precipitation method, followed by the produced nickel zinc ferrite nano particles nickel-zinc, iron ferrite magnetic ionic liquid, then add the Ni-Zn ferrite magnetic ionic liquid 3-methylthiophene monomer and initiator in situ polymerization of poly 3-methylthiophene well coated nano nickel zinc ferrite magnetic particles, and finally with Ni-Zn ferrite / poly 3-methylthiophene composite particles prepared poly 3-methylthiophene coated nano nickel zinc ferrite magnetic particles magnetic liquid.
Claims(1)  translated from Chinese
1. 一种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体的制备方法,其特征为: 其制备方法为: A、把31. 32gFe(N03)3 9Η20、12 89gNi(N03)2 6Η20、24 57gΖη(Ν03)2 6H20 溶解于250ml水中配置成溶液,再把12. 24gFeS04 7H20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70mL浓氨水,搅拌20-30分钟,然后磁分离4-6小时,用去离子水洗涤至ρΗ=7 0,把82. 02gFe(N03)3 9Η20溶解于500ml水中配置成Fe(N03)3 9Η20 溶液,把Fe(Ν03) 3 9Η20溶液倒入洗涤好的上述溶液中沸腾30-40分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉,即得纳米镍锌铁氧体粒子; Β、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91mol.L1的硝酸溶液配成1-2%的镍锌铁氧体Massart磁性液体,熟化6-8天; C、 在烧杯中加入已制备好的Massart磁性液体加水100ml稀释混合均勾后,将3ml3-甲基噻吩、0. 8ml硫酸和lg无水对氨基苯磺酸加入烧杯中,冰水浴3-4h,并在期间加入15%过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8mol/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; D、 取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. 8g十六烷基苯磺酸钠、2ml90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应24-26h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 1. A method for the preparation of poly-3-methyl-thiophene-coated nano nickel zinc ferrite magnetic particles in a liquid, wherein: the preparation method is: A, the 31. 32gFe (N03) 3 9Η20,12 89gNi (N03) 2 6Η20,24 57gΖη (Ν03) 2 6H20 dissolved in 250ml of water solution configured, then 12. 24gFeS04 7H20 dissolved in water to a solution of 250ml configured, the solution was poured into two or more three-necked flask dissolve after adding 70mL of concentrated aqueous ammonia, stirred for 20-30 minutes, 4-6 hours and then magnetically separated, washed with deionized water to ρΗ = 7 0, the 82. 02gFe (N03) 3 9Η20 arranged in 500ml of water was dissolved Fe ( N03) 3 9Η20 solution, the Fe (Ν03) 3 9Η20 good solution was poured into the above solution was washed with boiling for 30-40 minutes, to a magnetic separation cooled to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano-nickel-zinc ferrite particles; Β, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0 91mol.L1. nitric acid solution dubbed 1-2% nickel zinc ferrite magnetic fluid Massart, maturing 6-8 days; C, was added water 100ml diluted magnetic fluid has a good mix Massart hook are prepared in a beaker, it will 3ml3- a thiophene, 0. 8ml lg of anhydrous sulfuric acid and sulfanilic acid added to the beaker in an ice-water bath for 3-4h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after the reaction, with 0. 8mol / l sulfuric acid and acetone washed three times each, and washed with acetone to PH = 7, a nickel zinc ferrite / poly 3-methylthiophene composite particles; D, take one gram prepared Ni-Zn ferrite / poly 3 armor thiophene was added to the composite particles have 0. 8g hexadecyl benzene sulphonate, a mixed solution of 8ml 2ml90% ethanol and deionized water, and the reaction was stirred at room temperature for 24-26h, unable to remove even with a high speed centrifuge dispersed nickel zinc ferrite / poly 3-methylthiophene composite particles, whichever supernatant to obtain poly-3-methylthiophene-coated nano-nickel-zinc ferrite particles magnetic liquid.
Description  translated from Chinese
一种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体的制备方法 A process for preparing 3-methyl-thiophene-coated nano nickel zinc ferrite magnetic particles in a liquid poly

技术领域 TECHNICAL FIELD

[0001] 本发明涉及一种导电聚合物包裹纳米磁性颗粒磁性液体的制备方法,尤其涉及一种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体的制备方法。 [0001] The present invention relates to a method for preparing a conductive polymer nano-magnetic particles magnetic fluid inclusions, and particularly to a poly-3-methylthiophene-coated nano-nickel-zinc ferrite particles of magnetic fluid preparation.

背景技术 Background technique

[0002] 磁性液体是指尺寸量级小于单磁畴的纳米磁性颗粒高度弥散于液态基载液中而构成的一种高稳定性的胶体溶液,一般的磁性液体的分散剂是有机高分子链,不具备特殊的性能,而磁性液体中一旦在原先的纳米磁性颗粒和分散剂衔接处包裹上一层有机半导体后,一种新型的有机无机杂化磁性液体便应运而生,有机半导体通过与磁性液体有机结合后,有机半导体的性能便可通过调节磁场强度来使磁性液体具备规律性的光电性能变化, 因此该类新型磁性液体在微光器件和光子晶体等领域的应用上具有巨大潜力。 [0002] magnetic liquid refers to the size of the order of less than a single domain magnetic nano particles highly dispersed and formed in a high-stability of the colloidal solution of liquid-based carrier liquid, usually magnetic liquid dispersants are organic polymer chain , do not have special properties and magnetic liquid once in the original nano-magnetic particles and a dispersing agent convergence at the parcel after the organic semiconductor layer, a new type of organic-inorganic hybrid magnetic fluids have come into being, with the organic semiconductor after the magnetic liquid organic combination of properties of organic semiconductors can be by adjusting the magnetic field intensity of the magnetic fluid with regular optical and electrical properties change, so new kind of magnetic liquid has great potential in the field of devices and photonic crystals shimmer on the application.

[0003] 但是这类磁性液体的制备需要克服三个难点:一是导电聚3-甲基噻吩包裹磁性纳米铁氧体颗粒的稳定性;二是导电聚3-甲基噻吩包裹层的尺寸量级控制;三是包裹后的纳米磁性颗粒如何稳定分散于基载液中。 [0003] However, the preparation of such magnetic fluids need to overcome three difficulties: First, the stability of the conductive poly 3-methylthiophene parcel on the magnetic particles; the second is the size of the amount of conductive poly-3-methylthiophene batt level control; the third is wrapped after the nano-magnetic particles dispersed in the group how to stabilize the carrier liquid.

发明内容 SUMMARY

[0004] 本发明的目的是提供一种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体的制备方法,提高了导电聚3-甲基噻吩包裹磁性纳米铁氧体颗粒的稳定性,控制了导电聚3-甲基噻吩包裹层的尺寸量级,使得包裹后的纳米磁性颗粒稳定分散于基载液中。 [0004] The object of the present invention is to provide a poly-3-methylthiophene-coated preparing nano nickel zinc ferrite magnetic particles in a liquid to improve the stability of the conductive poly-3-methylthiophene parcel on the magnetic particles , control of the conductivity of poly 3-methylthiophene batt order of size, so that after the magnetic nanoparticles are dispersed in a stable package base carrier liquid.

[0005] -种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体,其制备方法为: [0005] - kind of poly-3-methylthiophene nickel-zinc ferrite particles coated with nano-magnetic fluid preparation method is:

[0006] A、把31. 32g Fe(NO3)3 9Η20、12 89g Ni (NO3)2 6Η20、24 57g Zn(NO3)2 6Η20溶解于250ml水中配置成溶液,再把12. 24g FeSO4 7Η20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70 mL浓氨水,搅拌20-30分钟,然后磁分离4-6小时,用去离子水洗涤至ρΗ=7 0,把82. 02g Fe(NO3)3 9Η20溶解于500ml水中配置成Fe(NO3)3 9Η20 溶液,把Fe (NO3) 3 9Η20溶液倒入洗涤好的上述溶液中沸腾30-40分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉,即得纳米镍锌铁氧体粒子; [0006] A, the 31. 32g Fe (NO3) 3 9Η20,12 89g Ni (NO3) 2 6Η20,24 57g Zn (NO3) 2 6Η20 configured dissolved in 250ml of water to the solution, and then 12. 24g FeSO4 7Η20 configured in 250ml of water was dissolved into a solution, the solution was poured into two or more concentrated aqueous ammonia was added after 70 mL three-neck flask was dissolved and stirred for 20-30 minutes, 4-6 hours and then magnetically separated, washed with deionized water until ρΗ = 7 0, to 82. 02g Fe (NO3) 3 9Η20 dissolved in 500ml water and configured to Fe (NO3) 3 9Η20 solution, the better the solution Fe (NO3) 3 9Η20 washed into the boiling solution 30-40 minutes, magnetically separated to cool to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano nickel-zinc ferrite particles ;

[0007] Β、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91 mol. L 1的硝酸溶液配成1-2%的镍锌铁氧体Massart磁性液体,熟化6-8天; [0007] Β, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0. 91 mol. L nitrate solution 1 dubbed 1-2% nickel zinc ferrite magnetic fluid Massart, aging 6 -8 days;

[0008] C、在烧杯中加入已制备好的Massart磁性液体加水100mL稀释混合均匀后,将3ml 3-甲基噻吩、0. 8ml硫酸和Ig无水对氨基苯磺酸加入烧杯中,冰水浴3-4h,并在期间加入15%过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8mol/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; [0008] C, was added in the beaker was prepared Massart 100mL magnetic liquid was diluted with water after mixing, the 3ml 3- methylthiophene, 0. 8ml of anhydrous sulfuric acid and Ig sulfanilic acid added to the beaker in an ice-water bath after 3-4h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after completion of the reaction, and washed three times with each 0. 8mol / l sulfuric acid and acetone, washed with acetone to PH = 7, a nickel zinc ferrite / poly 3-methylthiophene composite particles;

[0009] D、取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. Sg十六烷基苯磺酸钠、2ml 90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应24-26h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 [0009] D, taking 1 g prepared Ni-Zn ferrite / poly 3-methylthiophene was added to the composite particles have 0. Sg hexadecyl benzene sulfonate, 2ml 90% ethanol, deionized water and 8ml mixed solution after the reaction was stirred at room temperature for 24-26h, high-speed centrifuge to remove failed to uniformly disperse the Ni-Zn ferrite / poly 3-methylthiophene composite particles, whichever supernatant to obtain poly-3-methyl thiophene-coated nano-nickel-zinc ferrite particles magnetic liquid.

[0010] 本发明的优点是:本发明通过表面原位合成法将纳米镍锌铁氧体粒子用聚3-甲基噻吩包覆,达到聚3-甲基噻吩牢固包裹镍锌铁氧体纳米颗粒的效果,通过数学计算3-甲基噻吩单体数量,再辅以阻聚剂精确控制聚合度,防止3-甲基噻吩聚合度超过磁性液体所能承载的尺寸量级,控制在10-20纳米,从而达到控制镍锌铁氧体/聚3-甲基噻吩复合颗粒粒径的效果,获得磁性液体,同时也提高了导电聚3-甲基噻吩包裹磁性纳米铁氧体颗粒的稳定性(放置六个月不下沉)。 [0010] Advantages of the present invention are: The invention will be nano-nickel-zinc ferrite particles with poly-3-methylthiophene-coated surface by in situ synthesis, reach poly 3-methylthiophene securely wrapped nickel zinc ferrite nano the effect of the particles, by mathematical calculations the number of 3-methylthiophene monomer, a polymerization inhibitor supplemented by precise control of the degree of polymerization of 3-methyl-thiophene prevent polymerization degree exceeds the size of the magnetic fluid can carry the order of control in 10- 20 nm, so as to control the Ni-Zn ferrite / poly-methyl-thiophene composite particle size effect 3-, obtain magnetic liquid, but also improve the stability of the conductive poly-3-methylthiophene parcel on the magnetic particles (place six months does not sink). 该磁性液体由于有一层导电聚合物包覆层,因此其在规律性变化磁场作用下,其光电性能方面产生亦能的规律性变化,即最终达到通过调节磁场强度可控调节其在光电方面的性能指标的目的,在磁性液体的研究中开辟出了一个新颖的可供研究的小分支,具有很重要的研究及应用价值。 The magnetic liquid due to a layer of conductive polymer coating layer, so the regular changes in the magnetic field, the photoelectric performance can also generate regular changes that ultimately controlled by adjusting the magnetic field strength in the photovoltaic adjusted terms the purpose of performance indicators in the study of magnetic fluid in small branches opened up for a new study has very important research and application.

具体实施方式 detailed description

[0011] 结合上述发明内容提供以下实施案例。 [0011] The above summary provides the following binding implementation case.

[0012] 实施例1 : [0012] Example 1:

[0013] -种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体,其制备方法为: [0013] - kind of poly-3-methylthiophene nickel-zinc ferrite particles coated with nano-magnetic fluid preparation method is:

[0014] A、把31.32g Fe(N03)3.9H20、12.89g Ni(N03)2.6H20、24.57g Ζη(Ν03)26Η20 溶解于250ml水中配置成溶液,再把12. 24g FeSO4 7Η20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70 mL浓氨水,搅拌20分钟,然后磁分离4小时,用去离子水洗涤至pH=7. 0,把82. 02g Fe (NO3) 3 9H20溶解于500ml水中配置成Fe (NO3) 3 9H20 溶液,把Fe (NO3) 3 9H20溶液倒入洗涤好的上述溶液中沸腾30分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉, 即得纳米镍锌铁氧体粒子; [0014] A, the 31.32g Fe (N03) 3.9H20,12.89g Ni (N03) 2.6H20,24.57g Ζη (Ν03) 2 6Η20 dissolved in 250ml water solution configured, then 12. 24g FeSO4 7Η20 dissolved Configuring a solution in 250ml of water, the solution was poured into two or more three-neck flask was added after dissolution of 70 mL of concentrated aqueous ammonia, stirred for 20 minutes, 4 hours and then magnetically separated, washed with deionized water until pH = 7. 0, put 82. 02g Fe (NO3) 3 9H20 dissolved in 500ml of water arranged Fe (NO3) 3 9H20 solution to Fe (NO3) 3 9H20 solution was poured into the above solution was washed well boiled 30 minutes, cooled to a magnetic separation to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano-nickel-zinc ferrite particles;

[0015] B、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91 mol. L 1的硝酸溶液配成1%的镍锌铁氧体Massart磁性液体,熟化6天; [0015] B, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0 91 mol L 1 solution of nitric acid to form 1% nickel zinc ferrite magnetic fluid Massart, aging for 6 days.;

[0016] C、在烧杯中加入已制备好的Massart磁性液体加水100mL稀释混合均勾后,将3ml 3-甲基噻吩、0. 8ml硫酸和Ig无水对氨基苯磺酸加入烧杯中,冰水浴3h,并在期间加入15% 过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8m〇l/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; [0016] C, was added to the beaker has been prepared Massart magnetic liquid add water 100mL dilution were mixed hook, will 3ml 3- methylthiophene, 0. 8ml sulfuric acid and Ig anhydrous sulfanilic acid beaker, ice water bath for 3h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after completion of the reaction, and washed three times each with 0.1 8m〇l / l sulfuric acid and acetone, washed with acetone to PH = 7, a nickel zinc ferrite body / poly 3-methylthiophene composite particles;

[0017] D、取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. Sg十六烷基苯磺酸钠、2ml 90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应24h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 [0017] D, taking 1 g prepared Ni-Zn ferrite / poly 3-methylthiophene was added to the composite particles have 0. Sg hexadecyl benzene sulfonate, 2ml 90% ethanol, deionized water and 8ml the mixed solution, the reaction mixture was stirred at room temperature for 24h, it could not be removed with a high speed centrifuge uniformly dispersed nickel zinc ferrite / poly 3-methylthiophene composite particles, to obtain a supernatant whichever poly 3-methylthiophene package nano particles coated nickel zinc ferrite magnetic fluid.

[0018] 实施例2 : [0018] Example 2:

[0019] -种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体,其制备方法为: [0019] - kind of poly-3-methylthiophene nickel-zinc ferrite particles coated with nano-magnetic fluid preparation method is:

[0020] A、把31.32g Fe(N03)3.9H20、12.89g Ni(N03)2.6H20、24.57g Ζη(Ν03)26Η20 溶解于250ml水中配置成溶液,再把12. 24g FeSO4 7Η20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70 mL浓氨水,搅拌25分钟,然后磁分离5小时,用去离子水洗涤至pH=7. 0,把82. 02g Fe (NO3) 3 9H20溶解于500ml水中配置成Fe (NO3) 3 9H20 溶液,把Fe (NO3) 3 9H20溶液倒入洗涤好的上述溶液中沸腾35分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉, 即得纳米镍锌铁氧体粒子; [0020] A, the 31.32g Fe (N03) 3.9H20,12.89g Ni (N03) 2.6H20,24.57g Ζη (Ν03) 2 6Η20 dissolved in 250ml water solution configured, then 12. 24g FeSO4 7Η20 dissolved Configuring a solution in 250ml of water, the solution was poured into two or more concentrated aqueous ammonia was added after 70 mL three-neck flask was dissolved and stirred for 25 minutes, 5 hours and then magnetically separated, washed with deionized water until pH = 7. 0, put 82. 02g Fe (NO3) 3 9H20 dissolved in 500ml of water arranged Fe (NO3) 3 9H20 solution to Fe (NO3) 3 9H20 solution was poured into the above solution was washed well in boiling 35 minutes, cooled to a magnetic separation to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano-nickel-zinc ferrite particles;

[0021] B、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91 mol. L 1的硝酸溶液配成1. 5%的镍锌铁氧体Massart磁性液体,熟化6-8天; [0021] B, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0. 91 mol. L nitrate solution 1 dubbed 1.5% of nickel zinc ferrite magnetic fluid Massart, aging 6 -8 days;

[0022] C、在烧杯中加入已制备好的Massart磁性液体加水100mL稀释混合均匀后,将3ml 3-甲基噻吩、0. 8ml硫酸和Ig无水对氨基苯磺酸加入烧杯中,冰水浴3. 5h,并在期间加入15%过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8mol/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; [0022] C, was added in the beaker was prepared Massart 100mL magnetic liquid was diluted with water after mixing, the 3ml 3- methylthiophene, 0. 8ml of anhydrous sulfuric acid and Ig sulfanilic acid added to the beaker in an ice-water bath after 3. 5h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after completion of the reaction, and washed three times with each 0. 8mol / l sulfuric acid and acetone, washed with acetone to PH = 7, a nickel zinc ferrite / poly 3-methylthiophene composite particles;

[0023] D、取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. Sg十六烷基苯磺酸钠、2ml 90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应25h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 [0023] D, taking 1 g prepared Ni-Zn ferrite / poly 3-methylthiophene was added to the composite particles have 0. Sg hexadecyl benzene sulfonate, 2ml 90% ethanol, deionized water and 8ml the mixed solution, the reaction mixture was stirred at room temperature for 25H, could not be removed with a high speed centrifuge uniformly dispersed nickel zinc ferrite / poly 3-methylthiophene composite particles, to obtain a supernatant whichever poly 3-methylthiophene package nano particles coated nickel zinc ferrite magnetic fluid.

[0024] 实施例3 : [0024] Example 3:

[0025] -种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体,其制备方法为: [0025] - kind of poly-3-methylthiophene nickel-zinc ferrite particles coated with nano-magnetic fluid preparation method is:

[0026] A、把31.32g Fe(N03)3.9H20、12.89g Ni(N03)2.6H20、24.57g Ζη(Ν03)26Η20 溶解于250ml水中配置成溶液,再把12. 24g FeSO4 7Η20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70 mL浓氨水,搅拌30分钟,然后磁分离6小时,用去离子水洗涤至pH=7. 0,把82. 02g Fe (NO3) 3 9H20溶解于500ml水中配置成Fe (NO3) 3 9H20 溶液,把Fe (NO3) 3 9H20溶液倒入洗涤好的上述溶液中沸腾40分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉, 即得纳米镍锌铁氧体粒子; [0026] A, the 31.32g Fe (N03) 3.9H20,12.89g Ni (N03) 2.6H20,24.57g Ζη (Ν03) 2 6Η20 dissolved in 250ml water solution configured, then 12. 24g FeSO4 7Η20 dissolved Configuring a solution in 250ml of water, the solution was poured into two or more three-neck flask was added after dissolution of 70 mL of concentrated aqueous ammonia, stirred for 30 minutes, 6 hours and then magnetically separated, washed with deionized water until pH = 7. 0, put 82. 02g Fe (NO3) 3 9H20 dissolved in 500ml of water arranged Fe (NO3) 3 9H20 solution to Fe (NO3) 3 9H20 solution was poured into the above solution was washed well in boiling 40 minutes, cooled to a magnetic separation to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano-nickel-zinc ferrite particles;

[0027] B、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91 mol. L 1的硝酸溶液配成2%的镍锌铁氧体Massart磁性液体,熟化8天; [0027] B, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0 91 mol L nitrate solution dubbed 1 2% nickel zinc ferrite magnetic fluid Massart, curing 8 days..;

[0028] C、在烧杯中加入已制备好的Massart磁性液体加水100mL稀释混合均匀后,将3ml 3-甲基噻吩、0. 8ml硫酸和Ig无水对氨基苯磺酸加入烧杯中,冰水浴4h,并在期间加入15% 过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8m〇l/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; [0028] C, was added in the beaker was prepared Massart 100mL magnetic liquid was diluted with water after mixing, the 3ml 3- methylthiophene, 0. 8ml of anhydrous sulfuric acid and Ig sulfanilic acid added to the beaker in an ice-water bath after 4h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after completion of the reaction, and washed three times each with 0.1 8m〇l / l sulfuric acid and acetone, washed with acetone to PH = 7, a nickel zinc ferrite / poly 3-methylthiophene composite particles;

[0029] D、取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. Sg十六烷基苯磺酸钠、2ml 90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应26h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 [0029] D, taking 1 g prepared Ni-Zn ferrite / poly 3-methylthiophene was added to the composite particles have 0. Sg hexadecyl benzene sulfonate, 2ml 90% ethanol, deionized water and 8ml mixed solution after the reaction was stirred at room temperature for 26h, high-speed centrifuge to remove failed to uniformly disperse the Ni-Zn ferrite / poly 3-methylthiophene composite particles, whichever supernatant to obtain poly 3-methylthiophene package nano particles coated nickel zinc ferrite magnetic fluid.

[0030] 实施例4 : [0030] Example 4:

[0031 ] -种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体,其制备方法为: [0031] - kind of poly-3-methylthiophene nickel-zinc ferrite particles coated with nano-magnetic fluid preparation method is:

[0032] A、把31.32g Fe(N03)3.9H20、12.89g Ni(N03)2.6H20、24.57g Ζη(Ν03)26Η20 溶解于250ml水中配置成溶液,再把12. 24g FeSO4 7Η20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70 mL浓氨水,搅拌18分钟,然后磁分离3小时,用去离子水洗涤至pH=7. 0,把82. 02g Fe (NO3) 3 9H20溶解于500ml水中配置成Fe (NO3) 3 9H20 溶液,把Fe (NO3) 3 9H20溶液倒入洗涤好的上述溶液中沸腾25分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉, 即得纳米镍锌铁氧体粒子; [0032] A, the 31.32g Fe (N03) 3.9H20,12.89g Ni (N03) 2.6H20,24.57g Ζη (Ν03) 2 6Η20 dissolved in 250ml water solution configured, then 12. 24g FeSO4 7Η20 dissolved Configuring a solution in 250ml of water, the solution was poured into two or more three-neck flask was added after dissolution of 70 mL of concentrated aqueous ammonia, stirred for 18 minutes, then a magnetic separation 3 hours, washed with deionized water until pH = 7. 0, put 82. 02g Fe (NO3) 3 9H20 dissolved in 500ml of water arranged Fe (NO3) 3 9H20 solution to Fe (NO3) 3 9H20 solution was poured into the above solution was washed well in boiling 25 minutes, cooled to a magnetic separation to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano-nickel-zinc ferrite particles;

[0033] B、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91 mol. L 1的硝酸溶液配成1%的镍锌铁氧体Massart磁性液体,熟化6-8天; [0033] B, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0. 91 mol. L nitrate solution 1 to form 1% nickel zinc ferrite magnetic fluid Massart, ripening 6-8 day;

[0034] C、在烧杯中加入已制备好的Massart磁性液体加水100mL稀释混合均匀后,将3ml 3-甲基噻吩、0. 8ml硫酸和Ig无水对氨基苯磺酸加入烧杯中,冰水浴2h,并在期间加入15% 过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8m〇l/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; [0034] C, was added in the beaker was prepared Massart 100mL magnetic liquid was diluted with water after mixing, the 3ml 3- methylthiophene, 0. 8ml of anhydrous sulfuric acid and Ig sulfanilic acid added to the beaker in an ice-water bath after 2h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after completion of the reaction, and washed three times each with 0.1 8m〇l / l sulfuric acid and acetone, washed with acetone to PH = 7, a nickel zinc ferrite / poly 3-methylthiophene composite particles;

[0035] D、取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. Sg十六烷基苯磺酸钠、2ml 90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应20h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 [0035] D, taking 1 g prepared Ni-Zn ferrite / poly 3-methylthiophene was added to the composite particles have 0. Sg hexadecyl benzene sulfonate, 2ml 90% ethanol, deionized water and 8ml the mixed solution, the reaction mixture was stirred at room temperature for 20h, it could not be removed with a high speed centrifuge uniformly dispersed nickel zinc ferrite / poly 3-methylthiophene composite particles, to obtain a supernatant whichever poly 3-methylthiophene package nano particles coated nickel zinc ferrite magnetic fluid.

[0036] 实施例5 : [0036] Example 5:

[0037] -种聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体,其制备方法为: [0037] - kind of poly-3-methylthiophene nickel-zinc ferrite particles coated with nano-magnetic fluid preparation method is:

[0038] A、把31.32g Fe(N03)3.9H20、12.89g Ni(N03)2.6H20、24.57g Ζη(Ν03)26Η20 溶解于250ml水中配置成溶液,再把12. 24g FeSO4 7Η20溶解于250ml水中配置成溶液,把以上两种溶液倒入三口烧瓶中溶解后加入70 mL浓氨水,搅拌35分钟,然后磁分离7小时,用去离子水洗涤至pH=7. 0,把82. 02g Fe (NO3) 3 9H20溶解于500ml水中配置成Fe (NO3) 3 9H20 溶液,把Fe (NO3) 3 9H20溶液倒入洗涤好的上述溶液中沸腾45分钟,磁分离至自然冷却至室温,倒掉上层清液,用去离子水反复洗涤直至中性,在真空干燥皿中自然干燥,研磨成粉, 即得纳米镍锌铁氧体粒子; [0038] A, the 31.32g Fe (N03) 3.9H20,12.89g Ni (N03) 2.6H20,24.57g Ζη (Ν03) 2 6Η20 dissolved in 250ml water solution configured, then 12. 24g FeSO4 7Η20 dissolved Configuring a solution in 250ml of water, the solution was poured into two or more three-neck flask was added after dissolution of 70 mL of concentrated aqueous ammonia, stirred for 35 minutes, then magnetic separation seven hours, washed with deionized water until pH = 7. 0, put 82. 02g Fe (NO3) 3 9H20 dissolved in 500ml of water arranged Fe (NO3) 3 9H20 solution to Fe (NO3) 3 9H20 solution was poured into the above solution was washed well in boiling 45 minutes, cooled to a magnetic separation to room temperature, the supernatant was drained, washed repeatedly with deionized water until neutral, dried in a vacuum pan naturally dried, ground into powder, the nano-nickel-zinc ferrite particles;

[0039] B、取5克上述步骤所得纳米镍锌铁氧体粒子,加入94. 47ml0. 91 mol. L 1的硝酸溶液配成2%的镍锌铁氧体Massart磁性液体,熟化6-8天; [0039] B, take 5 g of the obtained nano-nickel-zinc ferrite particles, added 94. 47ml0. 91 mol. L nitrate solution dubbed 1 2% nickel zinc ferrite magnetic fluid Massart, ripening 6-8 day;

[0040] C、在烧杯中加入已制备好的Mas sart磁性液体加水I OOml稀释混合均匀后,将3ml 3-甲基噻吩、0. 8ml硫酸和Ig无水对氨基苯磺酸加入烧杯中,冰水浴5h,并在期间加入15% 过硫酸铵溶液20ml,反应结束后磁分离,并用0. 8m〇l/l硫酸和丙酮各洗三次后,用丙酮洗涤至PH=7,得镍锌铁氧体/聚3-甲基噻吩复合粒子; [0040] C, good Mas sart magnetic liquid into a beaker that had been prepared after dilution with water I OOml mix will 3ml 3- methylthiophene, 0. 8ml sulfuric acid and Ig anhydrous sulfanilic acid beaker, ice-water bath 5h, and during the addition of 15% ammonium persulfate solution 20ml, magnetic separation after completion of the reaction, and washed three times each with 0.1 8m〇l / l sulfuric acid and acetone, washed with acetone to PH = 7, a nickel zinc, iron oxygen / poly 3-methylthiophene composite particles;

[0041] D、取1克制备好的镍锌铁氧体/聚3-甲基噻吩复合粒子加入到有0. Sg十六烷基苯磺酸钠、2ml 90%乙醇和8ml去离子水的混合溶液中,室温下搅拌反应28h后,用高速离心机离心去除未能均匀分散的镍锌铁氧体/聚3-甲基噻吩复合粒子,取其上层液即得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体。 [0041] D, taking 1 g prepared Ni-Zn ferrite / poly 3-methylthiophene was added to the composite particles have 0. Sg hexadecyl benzene sulfonate, 2ml 90% ethanol, deionized water and 8ml mixed solution after the reaction was stirred at room temperature for 28h, high-speed centrifuge to remove failed to uniformly disperse the Ni-Zn ferrite / poly 3-methylthiophene composite particles, whichever supernatant to obtain poly 3-methylthiophene package nano particles coated nickel zinc ferrite magnetic fluid.

[0042] 各个实施例制得的聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体性能如下表所示: [0042] each coated nano-magnetic fluid performance nickel-zinc ferrite particles obtained in Example poly 3-methylthiophene embodiment shown in the following table:

[0043] [0043]

Figure CN103632798BD00071

[0044] 从以上数据可以看出,在本发明工艺范围内的实施例1-3制得聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体所能承载的尺寸量级,控制在10-20纳米,温度性良好,明显优于在本发明工艺范围外的实施例4、5,可见采用了本发明制备的聚3-甲基噻吩包覆纳米镍锌铁氧体粒子磁性液体性能具有良好的尺寸量级和稳定性,有重要的应用价值。 [0044] As can be seen from the above data, embodiments are within the scope of the invention process to obtain 1-3 poly 3-methylthiophene-coated nano-nickel-zinc ferrite particles of magnetic fluid can carry the size of the order, control 10-20 nm, the temperature is good, much better than in the process outside the scope of the invention. Examples 4 and 5, showing that the use of the present invention is the preparation of poly-3-methylthiophene-coated nano-nickel-zinc ferrite particles magnetic liquid performance has good dimensional stability and magnitude, there is an important value.

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Classifications
International ClassificationH01F1/44, H01F1/36
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