CN110818821A - Preparation method of organic-inorganic hybrid material of polystyrene palladium nanocube - Google Patents

Preparation method of organic-inorganic hybrid material of polystyrene palladium nanocube Download PDF

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CN110818821A
CN110818821A CN201911116800.9A CN201911116800A CN110818821A CN 110818821 A CN110818821 A CN 110818821A CN 201911116800 A CN201911116800 A CN 201911116800A CN 110818821 A CN110818821 A CN 110818821A
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polystyrene
inorganic hybrid
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seed crystal
palladium
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王哲
水天恩
朱阳阳
刘尧
李晨阳
陈文波
申洪城
孙强
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Changchun University of Technology
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Abstract

一种由硫氢键链接的聚苯乙烯钯纳米立方体的有机无机杂化材料PS‑SH@Pd及制备方法属于高分子自组装领域。本发明所要解决的技术问题是提供一种简单,高效,结构规整的聚合物负载体的制备方法,从而获得小粒径,大小均匀,结构一致,纳米级并易于携带催化剂,药物,荧光量子点等。该材料是以高分子的聚苯乙烯为主体,经过端基修饰,以四氢呋喃为溶剂合成的巯基封端的聚苯乙烯。再以表面活性剂为保护,采用柠檬酸钠,水合肼,硼氢化钠还原成小的晶种;然后用抗坏血酸,钯晶种进行介导生长,通过在其中加入卤素氯,溴,碘离子。可以诱导和抑制一些晶面的生长,从而生成稳定的{110}面为主导的面心立方体结构。最后经过2次的配体交换法,5次的离心沉淀洗涤制备PS‑SH@Pd。本发明的纳米粒子可在25nm±4nm‑110nm±4nm任意一个尺寸稳定存在。相关物质已经应用在药物控制释放,纳米探针,仪器传感以及作为碳碳键形成偶联反应和加氢反应的重要催化剂。An organic-inorganic hybrid material PS-SH@Pd of polystyrene palladium nanocubes linked by sulfur-hydrogen bonds and a preparation method belong to the field of polymer self-assembly. The technical problem to be solved by the present invention is to provide a simple, high-efficiency and regular structure of the preparation method of the polymer carrier, so as to obtain small particle size, uniform size, consistent structure, nano-scale and easy to carry catalysts, drugs, fluorescent quantum dots Wait. The material is a thiol-terminated polystyrene synthesized by using high-molecular polystyrene as the main body, modified by end groups and using tetrahydrofuran as a solvent. Then use surfactant as protection, use sodium citrate, hydrazine hydrate, sodium borohydride to reduce to small seed crystals; then use ascorbic acid, palladium seed crystals to mediate growth, by adding halogen chloride, bromine, iodide ions. The growth of some crystal planes can be induced and inhibited, resulting in a stable {110} plane-dominated face-centered cubic structure. Finally, PS-SH@Pd was prepared by 2 times of ligand exchange and 5 times of centrifugal precipitation and washing. The nanoparticle of the present invention can exist stably in any dimension of 25nm±4nm-110nm±4nm. Related substances have been used in controlled drug release, nanoprobes, instrumental sensing, and as important catalysts for carbon-carbon bond-forming coupling reactions and hydrogenation reactions.

Description

一种聚苯乙烯钯纳米立方体的有机无机杂化材料制备方法A kind of preparation method of organic-inorganic hybrid material of polystyrene palladium nano-cube

技术领域technical field

本发明属于高分子材料技术领域,特别涉及一种由硫氢键链接的聚苯乙烯钯纳米立方体的有机无机杂化材料及制备方法。The invention belongs to the technical field of polymer materials, in particular to an organic-inorganic hybrid material of polystyrene palladium nanocubes linked by sulfur-hydrogen bonds and a preparation method thereof.

背景技术Background technique

通过研究合成的理论和方法我们发现,嵌段共聚物与金属纳米粒子负载,在药物,催化,以及传感等众多领域都有实际的应用价值。近几年尤其在金纳米粒子与高聚物的自组装上有大量文献报道。以金纳米NPs为基础的药物载体采用偶联、配位、包覆等手段连接各种功能性药物,细胞和激素等配体,这类连接金的嵌段共聚物纳米载体与功能集团的相互作用进行对疾病的治疗手段被广泛的研究.各类金属粒子,稀土纳米晶体也在逐渐成为继金纳米之后成为广泛的研究对象,像Au、Ag、pt、pd、Fe磁性纳米等金属纳米粒子与高聚物形成有机无机的复合,极大的改善了分子链的疏水性的溶解性差,延长药物或催化剂的释放时间。By studying the theory and method of synthesis, we found that block copolymers loaded with metal nanoparticles have practical application value in many fields such as medicine, catalysis, and sensing. In recent years, there have been a lot of literature reports especially on the self-assembly of gold nanoparticles and polymers. The drug carrier based on gold nano-NPs uses coupling, coordination, coating and other means to connect various functional drugs, cells and hormones and other ligands. This kind of gold-connected block copolymer nanocarriers interact with functional groups. The treatment of diseases has been widely studied. Various metal particles and rare earth nanocrystals have gradually become the extensive research objects after gold nanoparticles, such as Au, Ag, pt, pd, Fe magnetic nanoparticles and other metal nanoparticles It forms an organic-inorganic compound with a high polymer, which greatly improves the hydrophobicity and poor solubility of the molecular chain, and prolongs the release time of drugs or catalysts.

近年来,金属纳米晶体与嵌段共聚物组装体系已经得到了广泛而深入的研究,现阶段,原位还原法制备的纳米晶体立体结构多样复杂,聚集态结构受制备条件影响较大,多种三维结构并存的金属晶体也影响到与药物或催化剂的链接与释放,而立方纳米晶体的研究还处于发展阶段。这就使得具有六个晶面相同等效的立方纳米晶体与嵌段共聚物的纳米体系在自组装的研究中,尤其是对控制释放,催化剂的精确运载,药物的缓释,以及在传感与探针的设计中对晶体规整的组装结构研究都具有广阔的发展空间和重要的研究意义。In recent years, the assembly system of metal nanocrystals and block copolymers has been extensively and deeply studied. At present, the three-dimensional structures of nanocrystals prepared by in-situ reduction methods are diverse and complex, and the aggregated structure is greatly affected by the preparation conditions. Metal crystals with coexisting three-dimensional structures also affect the linking and release with drugs or catalysts, while the research on cubic nanocrystals is still in the developmental stage. This makes the nanosystems with the same equivalent six crystal faces of cubic nanocrystals and block copolymers in self-assembly research, especially for controlled release, precise delivery of catalysts, sustained release of drugs, and in sensing and In the design of probes, the study of crystal regular assembly structure has broad development space and important research significance.

发明内容SUMMARY OF THE INVENTION

本发明对高分子有机无机纳米复合材料尺寸控制存在的不足,提供了一种由硫氢键链接的聚苯乙烯钯纳米立方体的有机无机杂化材料及制备方法。The invention provides an organic-inorganic hybrid material of polystyrene palladium nano-cubes linked by sulfur-hydrogen bonds and a preparation method for the deficiency of the size control of the polymer organic-inorganic nano-composite material.

该材料是以高分子的聚苯乙烯为主体,经过端基修饰,以四氢呋喃为溶剂合成的巯基封端的聚苯乙烯。再以表面活性剂十六烷基三甲基溴化铵(CTAB/CTAC)为保护,采用柠檬酸钠,水合肼,硼氢化钠还原成小的晶种;然后用抗坏血酸,CTAB和氯钯酸和钯晶种进行介导生长,通过在其中加入卤素氯,溴,碘离子。可以诱导和抑制一些晶面的生长,从而生成稳定的{110}面为主导的面心立方体结构。最后经过2次的配体交换法,5次的离心沉淀洗涤,制备出p2vp-sh@pd。本发明的纳米粒子可在25nm±4nm -110nm±4nm任意一个尺寸稳定存在。利用巯基封端的聚苯乙烯与pd纳米粒子之间的巯基相链接,使传统的利用分子间氢键的不稳定连接被取代,使pd纳米粒子更加稳定的固定在聚合物的链一端,从而可形成一种新型的负载体系。并且在这种两次配体交换法中,开始时利用氮氮-二甲基二乙基酰胺为溶剂,使大部分的pd立方纳米晶体被接入到硫氢键上,离心后再使用氯仿为溶剂第二次连接pd纳米立方晶,使得立方晶体的连接率大大增加。并且在氯仿的萃取之下,原来表面活性剂CTAB也一并萃取后离心除去。分离方便,产物纯净,并且方便收集。最后在氯仿中保存,成为随时可以使用或进行接枝的载体,性能稳定,相对均匀,纯度高。可在传感,医疗,药物,催化等多领域中进行应用。The material is a thiol-terminated polystyrene synthesized by using high-molecular polystyrene as the main body, modified by end groups and using tetrahydrofuran as a solvent. Then use the surfactant cetyltrimethylammonium bromide (CTAB/CTAC) as protection, use sodium citrate, hydrazine hydrate, sodium borohydride to reduce to small seeds; then use ascorbic acid, CTAB and chloropalladium acid and palladium seeds for mediated growth by adding halogen chloride, bromine, iodide ions. The growth of some crystal planes can be induced and inhibited, resulting in a stable {110} plane-dominated face-centered cubic structure. Finally, after 2 times of ligand exchange method and 5 times of centrifugal precipitation washing, p2vp-sh@pd was prepared. The nanoparticle of the present invention can exist stably in any dimension ranging from 25nm±4nm to 110nm±4nm. Using the thiol link between the thiol-terminated polystyrene and the pd nanoparticle, the traditional unstable connection using intermolecular hydrogen bonds is replaced, so that the pd nanoparticle is more stably fixed at one end of the polymer chain, so that it can be A new type of load system is formed. And in this double ligand exchange method, nitrogen-nitrogen-dimethyldiethylamide was used as solvent at the beginning, so that most of the pd cubic nanocrystals were connected to the sulfur-hydrogen bonds, and then chloroform was used after centrifugation. The second connection of the pd nanocubes for the solvent makes the connection rate of the cubic crystals greatly increased. And under the extraction of chloroform, the original surfactant CTAB was also extracted and removed by centrifugation. The separation is convenient, the product is pure, and the collection is convenient. Finally, it is stored in chloroform to become a carrier that can be used or grafted at any time, with stable performance, relatively uniform and high purity. It can be used in sensing, medical, pharmaceutical, catalysis and other fields.

附图说明:Description of drawings:

图1:复合材料制备流程图;Figure 1: Flow chart of composite material preparation;

图2:pd纳米粒子的红外测试图;Figure 2: Infrared test chart of pd nanoparticles;

图3:pd纳米粒子的紫外测试图;Figure 3: UV test chart of pd nanoparticles;

图4:pd纳米粒子的透射电镜透射与电子衍射测试图。Figure 4: Transmission electron microscope transmission and electron diffraction test images of pd nanoparticles.

具体实施方案:Specific implementation plan:

一种由硫氢键链接的聚苯乙烯钯纳米立方体的有机无机杂化材料,其制备过程如图1所示,包括以下步骤:An organic-inorganic hybrid material of polystyrene palladium nanocubes linked by sulfur-hydrogen bonds, the preparation process of which is shown in Figure 1, comprising the following steps:

步骤一:10 mM H2PdCl4 溶液配制:将 0.1773g PdCl2溶解于 10 ml, 0.2 mol/L 的盐酸溶液中,再加入 90ml 的二次蒸馏水,加热10min。Step 1: Preparation of 10 mM H 2 PdCl 4 solution: Dissolve 0.1773 g of PdCl 2 in 10 ml of 0.2 mol/L hydrochloric acid solution, add 90 ml of double distilled water, and heat for 10 min.

步骤二:将步骤一中10mM H2PdCl4溶液,取0.5ml加入到90℃油浴中的20 ml 10mM的 CTAC 溶液中。进行搅拌,转数800rmp。搅拌10分钟。Step 2: Add 0.5 ml of the 10 mM H2PdCl4 solution in Step 1 to 20 ml of 10 mM CTAC solution in an oil bath at 90°C. Stirring was carried out at 800 rpm. Stir for 10 minutes.

步骤三:加入 1ml 的10mM 的抗坏血酸水溶液。0.01ml 的10mM 的硼氢化钠水溶液,。0.01ml 的10mM 的柠檬酸钠水溶液。继续搅拌反应 30 分钟,在恒温30℃下保存,作为晶种。之后取不同该晶种来控制晶体大小。Step 3: Add 1ml of 10mM ascorbic acid in water. 0.01 ml of 10 mM sodium borohydride in water. 0.01 ml of 10 mM sodium citrate in water. Continue to stir the reaction for 30 minutes, and store it at a constant temperature of 30 °C as a seed crystal. This seed crystal is then taken to control the crystal size.

步骤四:将 0.5 ml 10mM 的 H2PdCl4溶液加入到10ml 50mM 的 CTAC溶液中,水浴加热,磁力搅拌2000rmp,然后加入不同量的立方纳米晶体。我们这里给出一个梯度的对比量。加入步骤三中的晶种50 ul标记为样品1;加入晶种250 ul标记为样品二;加入晶种500 ul标记为样品三;加入晶种1000 ul标记为样品四;加入晶种2000 ul标记为样品五;加入晶种3000 ul标记为样品六。Step 4: Add 0.5 ml of 10 mM H2PdCl4 solution to 10 ml of 50 mM CTAC solution, heat in a water bath, magnetically stir at 2000 rmp, and then add different amounts of cubic nanocrystals. We give a gradient contrast here. The 50 ul seed crystal added in step 3 is marked as sample 1; the 250 ul seed crystal added is marked as sample two; the seed crystal added with 500 ul is marked as sample three; the seed crystal added with 1000 ul is marked as sample four; the seed crystal added with 2000 ul is marked as sample four It is sample five; adding 3000 ul of seed crystals is marked as sample six.

步骤五:再加入0.5ml 10mM 的KI和1ml的10mM 的抗坏血酸水溶液。磁力搅拌2000rmp,水浴加热80℃,进行种子增长反应。Step 5: Add 0.5ml of 10mM KI and 1ml of 10mM ascorbic acid in water. Magnetic stirring was carried out at 2000 rmp, and the water bath was heated at 80 °C to carry out the seed growth reaction.

步骤六:纳米立方体的尺寸通过加入种子的量来调节,种子加入量与得到的相应纳米立方体的边长如下所示:标记样品1晶种50 ul为114nm;标记样品2晶种250 ul为81nm,标记样品3晶种500 ul为60nm ,标记样品4晶种1000 ul为46nm ,标记样品5晶种2000 ul为39nm ,标记样品6晶种3000 ul为28nm 。步骤七:反应结束后,将反应液在 12000 rpm 下离心 15 分钟。收集下层晶体。Step 6: The size of the nanocubes is adjusted by the amount of seeds added. The amount of seeds added and the side lengths of the corresponding nanocubes obtained are as follows: 50 ul of the labeled sample 1 seed crystal is 114 nm; 250 ul of the labeled sample 2 seed crystal is 81 nm , 500 ul of labeled sample 3 seed crystal is 60 nm, 1000 ul of labeled sample 4 seed crystal is 46 nm, 2000 ul of labeled sample 5 seed crystal is 39 nm, and 3000 ul of labeled sample 6 seed crystal is 28 nm. Step 7: After the reaction, centrifuge the reaction solution at 12,000 rpm for 15 minutes. Collect the lower crystals.

步骤八:超声条件下,将浓缩好的金纳米晶体(0.4ml-0.8ml)加入到ps-sh(10mg0.2mg/ml)的氯仿溶液中,30℃下持续超生30分钟,室温静置24小时。Step 8: Under ultrasonic conditions, add the concentrated gold nanocrystals (0.4ml-0.8ml) to the chloroform solution of ps-sh (10mg0.2mg/ml), continue to supergenerate at 30°C for 30 minutes, and let stand for 24 minutes at room temperature. Hour.

步骤九:离心12000rmp,30min 除去上层清液。Step 9: Centrifuge at 12000rmp for 30min to remove the supernatant.

步骤十:将第九步中离心后的液体分散在四氢呋喃中,经过三次沉淀和离心12000rmp,30min。然后再加入4mg的ps-sh(0.2mg/ml)重复相同的超生,熟化和纯化的过程。Step 10: Disperse the centrifuged liquid in the ninth step in tetrahydrofuran, and perform three precipitation and centrifugation at 12000 rmp for 30 min. Then 4 mg of ps-sh (0.2 mg/ml) was added to repeat the same process of supersonication, maturation and purification.

Claims (9)

1. A preparation method of polystyrene palladium nanocube organic-inorganic hybrid material comprises the following steps: preparation of 10mM H2PdCl4 solution (1), dispersion of H2PdCl4 solution in CTAC (2), preparation of Pd seed crystals (3), induction of Pd crystal growth of different sizes by using different Pd seed crystal concentrations (4), regulation of Pd crystal shape (5), selective covering of several sizes (6), separation, purification and concentration (7), and connection of polymer by two-time ligand exchange method (8).
2. The preparation method of the polystyrene palladium nanocube organic-inorganic hybrid material as claimed in claim 1, wherein the preparation of 10mM H2PdCl4 solution (1) is dissolved in 10ml of 0.2 mol/L hydrochloric acid solution, then 90ml of redistilled water is added, and the mixture is heated for 10 min.
3. The method for preparing organic-inorganic hybrid material of palladium nanocube of polystyrene as claimed in claim 1, wherein the dispersion of H2PdCl4 solution in CTAC (2), stirring at 800rmp for 10min in 20 ml 10mM CTAC solution in 90 ℃ oil bath.
4. The method for preparing an organic-inorganic hybrid material of polystyrene palladium nanocube according to claim 1, wherein the preparation of Pd seed crystal (3) comprises adding 1ml of 10mM ascorbic acid aqueous solution, 0.01ml of 10mM sodium borohydride aqueous solution, and 0.01ml of 10mM sodium citrate aqueous solution, continuing stirring reaction for 30 minutes, and storing at constant temperature of 30 ℃ as seed crystal.
5. The method for preparing organic-inorganic hybrid material of polystyrene palladium nanocube as claimed in claim 1, wherein different Pd seed crystal concentrations are used to induce the growth of Pd crystals with different sizes (4), 0.5ml 10mM KI and 1ml 10mM ascorbic acid aqueous solution are added, magnetic stirring is carried out at 2000rmp, water bath heating is carried out at 80 ℃, and seed growth reaction is carried out.
6. The method for preparing organic-inorganic hybrid material of palladium nanocubes polystyrene as claimed in claim 1, wherein the regulation of pd crystal shape (5), regulation of 10mM KI, standing growth and aging are continued for 30 minutes at 30 ℃, and standing is continued for 24 hours at room temperature.
7. A method for preparing organic-inorganic hybrid material of polystyrene palladium nanocubes, according to claim 1, characterized in that the selective coverage (6) of several sizes is adjusted by the amount of seeds added, the amount of seeds added is corresponding to the obtained nanocubes, the 50 ul seed crystal of labeled sample 1 is 114 nm; 250 ul of seed crystal of the marked sample 2 is 81nm, 500 ul of seed crystal of the marked sample 3 is 60nm, 1000 ul of seed crystal of the marked sample 4 is 46nm, 2000 ul of seed crystal of the marked sample 5 is 39nm, and 3000 ul of seed crystal of the marked sample 6 is 28 nm.
8. The method for preparing organic-inorganic hybrid material of polystyrene palladium nanocubes as claimed in claim 1, wherein the separation, purification and concentration (7) are performed, centrifugation is performed at 12000rmp for 30min, and supernatant is removed.
9. A method for preparing polystyrene palladium nanocube organic-inorganic hybrid material according to claim 1, characterized in that two times of ligand exchange method for connecting polymer (8), liquid after centrifugation is dispersed in tetrahydrofuran, and after three times of precipitation and centrifugation 12000rmp for 30min, 4mg of ps-sh (0.2 mg/ml) is added to repeat the same process of generating, curing and purifying.
CN201911116800.9A 2019-11-15 2019-11-15 Preparation method of organic-inorganic hybrid material of polystyrene palladium nanocube Pending CN110818821A (en)

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CN110115996A (en) * 2019-05-10 2019-08-13 中国科学技术大学 A kind of gold ruthenium nanocomposite and its synthetic method, golden ruthenium nanocomposite catalyst, application

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