WO2015096607A1 - 一种具有磁响应性的含poss原位复合纳米凝胶及其制备方法 - Google Patents

一种具有磁响应性的含poss原位复合纳米凝胶及其制备方法 Download PDF

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WO2015096607A1
WO2015096607A1 PCT/CN2014/093076 CN2014093076W WO2015096607A1 WO 2015096607 A1 WO2015096607 A1 WO 2015096607A1 CN 2014093076 W CN2014093076 W CN 2014093076W WO 2015096607 A1 WO2015096607 A1 WO 2015096607A1
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poss
peg
dpa
situ composite
magnetic responsiveness
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戴李宗
陈凌南
吴悦广
曾碧榕
毛杰
王爽
许一婷
罗伟昂
何凯斌
刘新瑜
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Xiamen University
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    • H01F1/0063—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use in a non-magnetic matrix, e.g. granular solids
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Definitions

  • the invention relates to a nanogel with magnetic responsiveness and a preparation method thereof, in particular to a POSS in-situ composite nanogel with magnetic responsiveness and a preparation method thereof.
  • Nanogel refers to a colloidal system with a particle size of 1 to 1000 nm and stable dispersion in water.
  • the molecular chain structure of the nanogel is between the branched polymer and the cross-linked network polymer, and the interior is a cross-linked network structure.
  • the cross-linking point between the molecular chains inside the nanogel can be either a chemical cross-linking point formed by a chemical bond or a physical cross-linking point formed by a weak interaction such as hydrogen bonding, electrostatic attraction or hydrophobic interaction.
  • Smart nanogels are nanogels that respond to external stimuli and are therefore known as stimuli-responsive nanogels. External stimuli usually include small ambient temperatures, changes in pH and ionic strength of the dispersion medium, as well as light, magnetic fields, specific chemicals or biological substances.
  • POSS Polyhedral Oligomeric Silsesquioxane
  • This method allows N-methacrylylated magnetic chitosan to be cured into a hydrogel under UV irradiation (30 to 120 seconds) and enables controlled assembly of a magnetic field induced patterned microgel assembly.
  • the process is more complicated and not suitable for practical applications.
  • the object of the present invention is to provide a POSS-containing in-situ composite nanogel having magnetic responsiveness and a preparation method thereof.
  • the POSS-containing in-situ composite nanogel is adsorbed by an amphiphilic macromolecule (POSS-MA-PEG-DPA) which is polymerizable and has a metal coordination complexing ability, and then is subjected to chemical coprecipitation.
  • the valence/trivalent iron salt precipitates in situ to form superparamagnetic Fe 3 O 4 particles, and finally a stable nanogel is obtained by adding a crosslinking agent to initiate polymerization.
  • the POSS-containing nanogel has a size of 100 to 300 nm, and the Fe 3 O 4 particle has a size of 5 to 15 nm and is uniformly dispersed in the polymer.
  • the preparation method of the POSS in-situ composite nanogel is as follows:
  • POSS-MA-PEG-DPA was dissolved in tetrahydrofuran (THF), and then slowly dropped into deionized water under ultrasonication, and THF was removed by rotary evaporation to obtain aqueous solution A containing POSS-MA-PEG-DPA.
  • THF tetrahydrofuran
  • the concentration of POSS-MA-PEG-DPA in the solution A was 0.1 to 2 mg/mL.
  • the concentration of the divalent iron salt is 0.5 ⁇ mol/L to 10 ⁇ mol/L
  • the concentration of the trivalent iron salt is 1.0 ⁇ mol/L to 20 ⁇ mol/L.
  • the crosslinking agent is N, N-methylenebisacrylamide, etc., and the amount is 0.1-1% by weight of POSS-MA-PEG-DPA; the initiator is ammonium persulfate, potassium persulfate, etc., and the dosage is 0.1-1.5. Wt%.
  • the molecular structure of the POSS-MA-PEG-DPA is as follows:
  • R is a POSS apex organic group
  • n is a degree of polymerization of polyethylene glycol
  • the POSS functional apex group is an aminopropyl group, and the remaining seven apical R groups are isobutyl groups.
  • the polyethylene glycol (PEG) has a molecular weight of 600 to 4000.
  • the preparation method of the POSS-MA-PEG-DPA is as follows:
  • POSS-MA, PEG, polymerization inhibitor and catalyst were dissolved in toluene, and reacted at 135 ° C for 36 h, then separated and purified to obtain POSS-MA-PEG.
  • the polymerization inhibitor is a phenol compound, an anthracene compound, an aromatic nitro compound or the like.
  • the separation and purification method is that after the solvent is distilled off by a rotary evaporator, extraction and precipitation are carried out using a petroleum ether/ether mixed solution having a volume ratio of 1:1, and the precipitate is separated by a centrifuge, and dried in a vacuum oven for 24 hours.
  • the catalyst is p-toluenesulfonic acid or concentrated sulfuric acid.
  • the polymerization inhibitor is used in an amount of 0.1 to 1% by weight based on the total amount of the monomers.
  • the catalyst is used in an amount of from 0.1 to 1% by weight based on the total amount of the monomers.
  • the present invention starts with a POSS-containing amphiphilic macromolecule having a polymerizable property and a metal coordination complexing ability, is complexed by adding an iron salt, and then is subjected to chemical coprecipitation to make the mixed divalent/trivalent iron salt Precipitation in situ, finally adding initiator and crosslinker to initiate polymerization to obtain magnetically responsive POSS-containing nanogels.
  • the method of the invention is simple and easy to operate, has simple preparation process, good controllability, and realizes nano gel environment
  • the combination of high performance and high mechanical properties has attractive application prospects in the fields of chemical mechanics, biomedicine and tissue engineering.
  • Figure 1 is a TEM image and high resolution TEM image of a POSS in-situ composite nanogel.
  • Figure 2 is an SEM image of a POSS in-situ composite nanogel.
  • Figure 3 is an XRD pattern of a POSS in-situ composite nanogel.
  • Figure 4 is a hysteresis loop diagram of a POSS in-situ composite nanogel.
  • Figure 5 is a graph of thermogravimetric analysis of a POSS in-situ composite nanogel.
  • POSS-MA-PEG1000-DPA 0.50g POSS-MA-PEG1000-DPA was dissolved in 10mL THF to obtain the mixture A; 250 ⁇ L of the solution A was slowly dropped into 10mL of deionized water under ultrasonication, and the THF was obtained by rotary evaporation to obtain POSS-MA-PEG1000-DPA. Aqueous solution.
  • the average particle diameter of the nanogel measured by DLS was 255.8 nm, and the specific saturation magnetic strength of the micelle was 32.9 emu/g as measured by a SQUID superconducting quantum interference magnetometer.
  • the molecular weight of the PEG in the step (1) was changed to 600, 2000, and 4000, respectively, and the results are shown in Table 1.
  • the amount of the mixed iron salt in the step (3) was changed to 100 ⁇ L, 300 ⁇ L, 400 ⁇ L, and 500 ⁇ L, and the results are shown in Table 2.
  • Example Micellar particle size (nm) Micelle ratio saturation magnetic strength (emu/g) 2 235.4 31.6 3 267.8 33.8 4 296.9 31.2
  • Example Micellar particle size (nm) Micelle ratio saturation magnetic strength (emu/g) 5 254.3 22.4 6 258.7 43.1 7 266.9 54.7 8 272..8 66.5
  • the invention has reasonable design, feasible process and simple operation, and the prepared nanogel magnetic particles are uniformly dispersed and have good magnetic responsiveness.

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Abstract

本发明提供了一种具有磁响应性的含POSS原位复合纳米凝胶及其制备方法，涉及一种复合材料及其制备方法。本发明设计合成了一种含POSS双亲大分子，不仅具有可聚合性，而且对金属粒子具有配位络合能力。通过添加铁盐与之络合，然后采用化学共沉淀法使混合的二价/三价铁盐在原位沉淀，最后再添加引发剂、交联剂引发聚合得到具有磁响应性的含POSS纳米凝胶。本发明设计合理、工艺可行、操作简单，且所制备的纳米凝胶磁性粒子分散均匀，磁响应性好，在医学诊断、传感器、催化剂载体、生物材料等领域具有广泛的应用价值。

Description

一种具有磁响应性的含POSS原位复合纳米凝胶及其制备方法 技术领域
本发明涉及一种具有磁响应性的纳米凝胶及其制备方法，特别是一种具有磁响应性的含POSS原位复合纳米凝胶及其制备方法。
背景技术
纳米凝胶是指粒径在1～1000nm，能稳定分散在水中的胶体体系。纳米凝胶的分子链结构介于支化聚合物和交联网状聚合物之间，内部为交联网状结构。纳米凝胶内部分子链之间的交联点既可以是由化学键形成的化学交联点，也可以是通过氢键、静电吸引或疏水相互作用等弱相互作用形成的物理交联点。智能纳米凝胶是能对外界刺激产生响应的纳米凝胶，因此又被称为刺激响应性纳米凝胶。外界刺激通常包括微小的环境温度、分散介质pH和离子强度的变，以及光、磁场、特定的化学物质或生物物质等。
多面体齐聚倍半硅氧烷(Polyhedral Oligomeric Silsesquioxane，简称POSS)是一类笼状结构的有机/无机杂化分子，具有超疏水性、大位阻效率及纳米尺度，并表现出特殊的热学、光学、磁学和声学性质。POSS基聚合物材料被誉为“新一代高性能聚合物材料”。
近十年来，随着纳米科技、生物医学和智能材料的发展，智能纳米凝胶显示出诱人的应用前景，因此对其制备方法、结构与性能的关系以及应用领域的研究受到越来越多人的关注。在这一领域，张天柱等(一种含磁性纳米粒子的壳聚糖水凝胶的制备方法，中国专利，公开号：CN 102766267A)往壳聚糖乙酸溶液中添加磁性纳米粒子分散液，再添加交联剂反应生成含磁性纳米粒子的壳聚糖水凝胶。采用包埋法简单便捷，但是存在由于磁性纳米粒子在形成凝胶过程中易发生团聚和沉淀而引起磁性分布不均的问题。陈咏梅等(一种新型磁性高分子水凝胶的制备方法，中国专利，公开号：CN 102391603A)在磁性高分子水凝胶的形成过程中，利用静电相互作用使铁离子被水凝胶中的磺酸根吸附，再通过简单温和的共沉淀法使铁离子沉淀生成尺寸50nm～100nm的Fe3O4磁性颗粒。这种方法 在一定程度上克服了磁性分布不均匀的问题，但是所得凝胶体系粒径较大，在生物医药领域的应用受到一定的限制。万锕俊等(一种温度、pH及磁场三重敏感性的复合微凝胶的制备方法，中国专利，公开号：CN 103242494A)具有超顺磁性的纳米四氧化三铁颗粒，并在其表面形成了引发中心，使温敏和pH敏单体进行沉降聚合反应将其包覆，制得纳米四氧化三铁被包覆的同时具有温度、pH及磁场三重敏感性的复合微凝胶。这种方法同样存在磁性分布不均匀的问题。李保强等(一种可UV固化且可溶于水的磁性壳聚糖水凝胶的制备方法，中国专利，公开号：CN 103304826A)公开了一种磁性壳聚糖水凝胶的制备方法。这种方法可以使N-甲基丙烯酰化磁性壳聚糖在UV辐照下(30～120秒)固化为水凝胶，且可实现磁场诱导图案化微凝胶组装体的可控组装，但是工艺较为复杂，不适合实际应用。
目前，具有磁响应性的含POSS原位复合纳米凝胶尚未见报道。
发明内容
本发明目的在于提供一种具有磁响应性的含POSS原位复合纳米凝胶及其制备方法。
所述含POSS原位复合纳米凝胶由一种可聚合的且具有金属配位络合能力的双亲大分子(POSS-MA-PEG-DPA)通过吸附铁盐，然后采用化学共沉淀法使二价/三价铁盐在原位沉淀，生成超顺磁Fe3O4粒子，最后在加入交联剂引发聚合得到稳定的纳米凝胶。含POSS纳米凝胶尺寸为100～300nm，Fe3O4粒子尺寸为5～15nm且均匀分散在聚合物中。
所述含POSS原位复合纳米凝胶的制备方法如下：
(1)将POSS-MA-PEG-DPA溶于四氢呋喃(THF)中，然后在超声作用下缓慢滴入去离子水中，旋蒸除去THF后得到含POSS-MA-PEG-DPA的水溶液A。
(2)将含有Fe2+/Fe3+的铁盐溶液逐滴滴入溶液A中，搅拌0.5～3小时后，滴入NaOH溶液，得溶液B。
(3)在溶液B中添加交联剂、引发剂，升温至50～70℃，反应2～12小时，得到具有磁响应性的含POSS原位复合纳米凝胶。
所述溶液A中POSS-MA-PEG-DPA的浓度为0.1～2mg/mL。
所述铁盐溶液中，二价铁盐的浓度为0.5μmol/L～10μmol/L，三价铁盐的浓度为1.0μmol/L～20μmol/L。
所述交联剂为N，N-亚甲基双丙烯酰胺等，用量为POSS-MA-PEG-DPA的0.1～1wt％；引发剂为过硫酸铵、过硫酸钾等，用量为0.1～1.5wt％。
所述POSS-MA-PEG-DPA的分子结构如下：
Figure PCTCN2014093076-appb-000001
其中R为POSS顶角有机基团，n为聚乙二醇的聚合度。
所述POSS官能顶角基团为氨丙基，其余七个顶角R基为异丁基。
所述聚乙二醇(PEG)分子量为600～4000。
所述POSS-MA-PEG-DPA的制备方法如下：
(1)将氨丙基POSS、马来酸酐(MA)以及阻聚剂溶解于甲苯中，在90℃下反应24h后分离提纯得到POSS-MA。
(2)将POSS-MA、PEG、阻聚剂、催化剂溶解于甲苯中，在135℃下反应36h后分离提纯得到POSS-MA-PEG。
(3)将POSS-MA-PEG、2，6-吡啶二甲酸(DPA)、阻聚剂、催化剂溶解于1，4-二氧六环，在125℃下反应24h后分离提纯得到POSS-MA-PEG-DPA。
所述阻聚剂为酚类化合物、醌类化合物、芳香族硝基化合物等。
所述分离提纯方法为用旋蒸仪蒸除溶剂后，使用体积比为1∶1的石油醚/乙醚混合溶液进行萃取沉淀，再用离心机分离沉淀，置于真空烘箱中干燥24h。
所述催化剂为对甲苯磺酸或浓硫酸。
所述阻聚剂用量为占单体总量0.1～1wt％。
所述催化剂用量为占单体总量0.1～1wt％。
本发明以具有可聚合性质及金属配位络合能力的含POSS双亲大分子为起始，通过添加铁盐与之络合，然后采用化学共沉淀法使混合的二价/三价铁盐在原位沉淀，最后再添加引发剂、交联剂引发聚合得到具有磁响应性的含POSS纳米凝胶。本发明方法简单易行、制备工艺简单、可控性好，实现纳米凝胶环境响 应性与高力学性能的结合，在化学机械、生物医学及组织工程等领域具有诱人的应用前景。
附图说明
图1为含POSS原位复合纳米凝胶的TEM图及高分辨TEM图。
图2为含POSS原位复合纳米凝胶的SEM图。
图3为含POSS原位复合纳米凝胶的XRD图。
图4为含POSS原位复合纳米凝胶的磁滞回线图。
图5为含POSS原位复合纳米凝胶的热失重图。
具体实施方式
下面通过实施例对本发明做进一步说明。
实施例1
(1)双亲大分子POSS-MA-PEG-DPA的制备
将6gPOSS、0.67g马来酸酐(MA)、0.034g对苯二酚及50mL甲苯混溶均匀，在90℃下反应24h后分离提纯得到POSS-MA；将1gPOSS-MA、2.05gPEG1000、0.011g对甲苯磺酸、0.0187g对苯二酚及50mL甲苯混溶均匀，通氮气，在135℃下反应24h后分离提纯得到POSS-MA-PEG1000；将2gPOSS-MA-PEG1000、0.078g 2，6-吡啶二甲酸(DPA)、0.0054g对甲苯磺酸、0.0096g对苯二酚及50mL 1，4-二氧六环混溶均匀，在125℃下反应24h后分离提纯得到POSS-MA-PEG2000-DPA。
(2)含POSS原位复合纳米凝胶的制备
0.50g POSS-MA-PEG1000-DPA溶于10mL THF中得混合液A；取250μL溶液A在超声作用下缓慢逐滴滴入10mL去离子水中，旋蒸除去THF后得POSS-MA-PEG1000-DPA水溶液。
2.73g FeCl3·6H2O、1.45g FeSO4·7H2O溶于100mL去离子水中得到二价铁/三价铁混合液；取100μL混合铁盐溶液逐滴滴入上述POSS-MA-PEG1000-DPA水溶液，搅拌1小时后加入100μL浓度为0.44mol/L继续搅拌1小时；加入0.012g N，N-亚甲基双丙烯酰胺，0.009g过硫酸铵，升温至60℃反应6小时得到含POSS 原位复合纳米凝胶。
由DLS测得纳米凝胶的平均粒径为255.8nm，由SQUID超导量子干涉磁强计测得胶束的比饱和磁强度为32.9emu/g。
实施例2～4
同实施例1工艺，改变步骤(1)中PEG的分子量分别为600、2000、4000，得到结果如表1。
实施例5～8
同实施例1工艺，改变步骤(3)中混合铁盐的投料量为100μL、300μL、400μL、500μL，得到结果如表2。
表1
实施例 胶束粒径(nm) 胶束比饱和磁强度(emu/g)
2 235.4 31.6
3 267.8 33.8
4 296.9 31.2
表2
实施例 胶束粒径(nm) 胶束比饱和磁强度(emu/g)
5 254.3 22.4
6 258.7 43.1
7 266.9 54.7
8 272..8 66.5
工业实用性
本发明设计合理、工艺可行、操作简单，且所制备的纳米凝胶磁性粒子分散均匀，磁响应性好。

Claims (8)

  1. 一种具有磁响应性的含POSS原位复合纳米凝胶，其特征在于含POSS原位复合纳米凝胶由一种可聚合的且具有金属配位络合能力的双亲大分子(POSS-MA-PEG-DPA)通过吸附铁盐，然后采用化学共沉淀法使二价/三价铁盐在原位沉淀，生成超顺磁Fe3O4粒子，在加入交联剂引发聚合得到稳定的纳米凝胶；含POSS纳米凝胶尺寸为100～300nm，Fe3O4粒子尺寸为5～15nm且均匀分散在聚合物中。
  2. 根据权利要求1所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述含POSS原位复合纳米凝胶的制备方法如下：
    (1)将POSS-MA-PEG-DPA溶于四氢呋喃(THF)中，然后在超声作用下缓慢滴入去离子水中，旋蒸除去THF得到含POSS-MA-PEG-DPA的水溶液A；
    (2)将含有Fe2+/Fe3+的铁盐溶液逐滴滴入溶液A中，搅拌0.5～3小时后，滴入NaOH溶液，得溶液B；
    (3)在溶液B中添加交联剂、引发剂，升温至50～70℃，反应2～12小时，得到具有磁响应性的含POSS原位复合纳米凝胶。
  3. 根据权利要求2所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述溶液A中POSS-MA-PEG-DPA的浓度为0.1～2mg/mL。
  4. 根据权利要求2所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述的铁盐溶液中，二价铁盐的浓度为0.5μmol/L～10μmol/L，三价铁盐的浓度为1.0μmol/L～20μmol/L。
  5. 根据权利要求2所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述交联剂为N，N-亚甲基双丙烯酰胺等，用量为POSS-MA-PEG-DPA的0.1～1wt％；引发剂为过硫酸铵或过硫酸钾，用量为0.1～1.5wt％。
  6. 根据权利要求2所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述POSS-MA-PEG-DPA的分子结构如下：
    Figure PCTCN2014093076-appb-100001
    其中R为POSS顶角有机基团，n为聚乙二醇的聚合度；
    所述POSS官能顶角基团为氨丙基，其余七个顶角R基为异丁基。
  7. 根据权利要求2所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述聚乙二醇(PEG)分子量为600～4000。
  8. 根据权利要求2或6所述的一种具有磁响应性的含POSS原位复合纳米凝胶的制备方法，其特征在于所述POSS-MA-PEG-DPA的制备方法如下：
    (1)将氨丙基POSS、马来酸酐(MA)以及阻聚剂溶解于甲苯中，在90℃下反应24h后分离提纯得到POSS-MA；
    (2)将POSS-MA、PEG、阻聚剂、催化剂溶解于甲苯中，在135℃下反应36h后分离提纯得到POSS-MA-PEG；
    (3)将POSS-MA-PEG、2，6-吡啶二甲酸(DPA)、阻聚剂、催化剂溶解于1，4-二氧六环，在125℃下反应24h后分离提纯得到POSS-MA-PEG-DPA。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117466599A (zh) * 2023-11-01 2024-01-30 宿迁华美新材料有限公司 一种抗腐蚀预制混凝土方桩
CN120022427A (zh) * 2025-02-20 2025-05-23 武汉大学中南医院 一种脱细胞猪心包与poss-peg-cho交联的生物纳米复合材料及其制备方法和应用

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940210B (zh) * 2018-02-08 2021-04-13 陕西科技大学 磁性Fe3O4-POSS-COOH功能化纳米吸附材料及其制备方法
CN109010014B (zh) * 2018-08-08 2020-09-22 武汉中投汉嘉科技有限公司 耳穴压丸及其制备方法
CN110624519B (zh) * 2019-10-16 2022-11-22 盐城神华机械制造有限公司 一种磁性强、疏水性高的壳聚糖-硬脂酸复合吸油材料
CN113480745B (zh) * 2021-04-16 2022-07-12 山东师范大学 一种超拉伸磁响应自修复水凝胶及其制备方法、应用
CN114957716B (zh) * 2022-03-16 2025-04-18 东南大学 一种可磁控驱动的负温敏性水凝胶及其制备方法和应用
CN118652390B (zh) * 2024-07-06 2026-01-27 青岛科技大学 一种利用低聚倍半硅氧烷制备的超分子纳米复合自修复水凝胶

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432972A (zh) * 2011-09-28 2012-05-02 东华大学 一种具有磁性功能的纳米复合水凝胶的制备方法
CN103435951A (zh) * 2013-09-09 2013-12-11 江南大学 一种纳米复合高分子双网络水凝胶及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8353410B2 (en) * 2009-11-24 2013-01-15 International Business Machines Corporation Polymeric films made from polyhedral oligomeric silsesquioxane (POSS) and a hydrophilic comonomer
JP5960396B2 (ja) * 2011-06-30 2016-08-02 国立大学法人信州大学 ナノカプセルの製造方法
CN103013091B (zh) * 2012-12-21 2016-05-11 厦门大学 一种poss基封端具有金属离子敏感性的双亲纳米胶束及其制备方法
CN103113735B (zh) * 2013-02-04 2015-05-20 厦门大学 一种纳米贵金属/含poss聚合物杂化微球及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432972A (zh) * 2011-09-28 2012-05-02 东华大学 一种具有磁性功能的纳米复合水凝胶的制备方法
CN103435951A (zh) * 2013-09-09 2013-12-11 江南大学 一种纳米复合高分子双网络水凝胶及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEN, LINGNAN ET AL.: "A Metal-Sensitive Organic-Inorganic Hybrid Surfactant: POSS-Capped Dipicolinic Acid-Functionalized Poly (Ethylene Glycol) Amphiphile", REACTIVE & FUNCTIONAL POLYMERS, vol. 8, no. 73, 31 August 2013 (2013-08-31), pages 1022 *
ZENG, BIRONG ET AL.: "Preparation and Superparamagnetic Property of the Fe3O4/Polymer Composite Microsphere", PROCEEDINGS OF THE 17 TH NATIONAL MAGNETIC RESONANCE CONFERENCE, 24 October 2012 (2012-10-24) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117466599A (zh) * 2023-11-01 2024-01-30 宿迁华美新材料有限公司 一种抗腐蚀预制混凝土方桩
CN117466599B (zh) * 2023-11-01 2024-05-07 宿迁华美新材料有限公司 一种抗腐蚀预制混凝土方桩
CN120022427A (zh) * 2025-02-20 2025-05-23 武汉大学中南医院 一种脱细胞猪心包与poss-peg-cho交联的生物纳米复合材料及其制备方法和应用

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