WO2022236509A1 - 一种室温下制备石墨烯基碳纤维的方法 - Google Patents

一种室温下制备石墨烯基碳纤维的方法 Download PDF

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WO2022236509A1
WO2022236509A1 PCT/CN2021/092511 CN2021092511W WO2022236509A1 WO 2022236509 A1 WO2022236509 A1 WO 2022236509A1 CN 2021092511 W CN2021092511 W CN 2021092511W WO 2022236509 A1 WO2022236509 A1 WO 2022236509A1
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acid
graphene oxide
graphene
fibers
room temperature
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PCT/CN2021/092511
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French (fr)
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高超
王子秋
李鹏
许震
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浙江大学
杭州高烯科技有限公司
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Priority to PCT/CN2021/092511 priority Critical patent/WO2022236509A1/zh
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof

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  • the invention relates to the field of nanomaterials, in particular to a method for preparing graphene-based carbon fibers using two-dimensional graphene oxide as a precursor at room temperature.
  • graphene oxide itself has a two-dimensional structure, and has a high carbon content and carbon structure ratio. In theory, it has a low reduction activation energy, so it is easier to reduce to obtain high-quality carbon. structural fibers. Compared with traditional carbon fibers, the preparation of carbon fibers from graphene oxide is expected to be realized under lower energy conditions.
  • the present invention aims to provide a method for preparing graphene-based carbon fibers at room temperature. After simple chemical reduction, the graphene fiber has a carbon content of more than 90%, which meets the standard of carbon fiber, and has mechanical properties comparable to traditional carbon fiber and better thermal conductivity.
  • the present invention is aimed at graphene oxide, a two-dimensional planar macromolecule, whose huge aspect ratio makes it have good lyotropic liquid crystal phenomenon, and the huge molecule makes the dynamic stability of the liquid crystal good, so that the microfibrillation structure can be carried out design.
  • the present invention obtains microfibrillated graphene oxide fibers by setting partitioned flow channels.
  • the graphene oxide spinning solution with a liquid crystal state is cut into numerous microfibrillated structures by the splitter grid at the front end of the spinning tube, and the microfibrillated structure is maintained in the spinning tube. This microfibrillated structure continues to be retained after subsequent plasticizing and stretching, and the degree of orientation is greatly improved by stretching.
  • the present invention adopts following technical scheme:
  • the partitioned flow channel includes a spinning tube and a split grid vertically arranged at the front section of the spinning tube; the graphene oxide spinning solution passes through the split grid Cut into numerous microfibrillated structures, and maintain the microfibrillated structure in the back section of the spinning tube;
  • the graphene oxide liquid crystal of the microfibrillated structure obtained in step 1 is first extruded into the coagulation bath to obtain primary microfibrillated graphene oxide fibers. Then it is drawn into the stretching bath, soaked to make it plasticized, and the plasticization increases the interlayer distance of graphene oxide, and the interlayer distance is controlled at 1.1-1.8nm to achieve the best effect of plastic deformation. When the interlayer distance continues to increase, the macroscopic fibers are easily broken because the interlayer interaction is too weak, leading to slippage between the graphene oxide layers.
  • the shape of the spinning tube in step 1 is circular; the grid shape of the distribution grid includes but is not limited to circular, square, triangular, hexagonal and various complex shapes.
  • the spinning solution described in step 1 is a graphene oxide aqueous phase dispersion, DMF phase dispersion, DMAc phase dispersion, and DMSO phase dispersion.
  • the coagulation bath described in step 2 is ethyl acetate, dichloromethane, acetic acid, ethanol, water, isopropanol, chloroform, acetone, etc. and a mixed coagulation bath thereof.
  • the stretching bath described in step 2 is ethanol, acetone, isopropanol, acetic acid, ethyl acetate, methanol, water, glycerol, propylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, penta Ethylene glycol, hydrochloric acid, organic amine, etc. or their mixed solvents.
  • step 3 should be carried out more than 3 times.
  • the reagents used in the chemical reduction described in step 4 are hydroiodic acid and ethanol, acetic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, dibromoacetic acid , tribromoacetic acid, iodoacetic acid, diiodoacetic acid, triiodoacetic acid mixed solution, or hydrazine hydrate, sodium ascorbate, stannous chloride, etc.
  • the beneficial effect of the present invention lies in: the present invention uses graphene oxide as the precursor of carbon fiber, based on the method of wet liquid crystal spinning, regulates the fiber structure with partitioned channels, passes through the plastic processing interval of 1 to 50%, and is equipped with continuous Stretching in a chemical reduction bath and sufficient and efficient chemical reduction at room temperature can prepare graphene-based carbon fibers with excellent properties. After reduction, the carbon content reaches more than 90%. Compared with high-strength PAN-based carbon fibers, the strength can reach 5.5GPa, the modulus is 240GPa, and the toughness is 75MJ/m 3 .
  • the strength is comparable to that of T800 series high-strength carbon fibers, and has better toughness;
  • the thermal conductivity reaches 230W/(m ⁇ K), which has obvious advantages;
  • the electrical conductivity is 1.3*10 4 S/m, which is similar to it.
  • the graphene-based carbon fiber of the present invention does not require heat treatment throughout the entire process, is environmentally friendly, greatly reduces costs and achieves high performance.
  • Fig. 1 is an enhanced flowchart of the present invention.
  • Fig. 2 shows the microfibrillation structure characteristics of the graphene oxide liquid crystal in the spinning tube after freeze-drying.
  • Figure 3 is the typical mechanical curves of three kinds of graphene fibers and T-800 carbon fibers, Control is the fiber without microfibrillation; GF-100 and GF-30 are the microfibrillation prepared from 100 micron and 30 micron graphene oxide raw materials respectively Structured graphene fibers.
  • Figure 4 shows the in-situ test results of the electrical conductivity of the fibers during reduction under different reduction conditions.
  • Graphene oxide with an average sheet diameter of 100 microns is prepared into 8 mg/g DMF phase spinning solution, squeezed into an ethyl acetate coagulation bath through a circular spinning tube with a diameter of 100 ⁇ m, and obtained by wet liquid crystal spinning Nascent graphene oxide fibers; in this embodiment, a shunt grid is set in the circular spinning tube, and the liquid crystal spinning solution is divided into numerous microfiber structures by passing through the device of the shunt grid.
  • the grid shape of the shunt grid is square, and the single hole size is 10 microns.
  • the nascent graphene oxide fiber is continuously drawn into the stretching bath prepared by acetic acid and water according to the volume ratio of 5:1, 3:1, and 1:1 for continuous three-stage stretching, and the total stretching ratio is 50 %.
  • plasticization increases the interlayer spacing of graphene oxide to 1.2–1.4 nm.
  • the fiber is continuously passed through a reduction bath prepared by hydroiodic acid and trifluoroacetic acid in a volume ratio of 1:6.
  • the temperature of the reduction bath is 25 degrees, and the fiber is subjected to tensile stress for 5 minutes. chemical reduction.
  • the graphene-based carbon fiber prepared at room temperature in Example 1 can reach a strength of 5.5GPa, a modulus of 240GPa, an elongation at break of 2.3%, and a toughness of 75MJ/m 3 , as shown in Figure 3
  • the thermal conductivity reaches 230W/(m ⁇ K); the electrical conductivity is 1.3*10 4 S/m.
  • the carbon content reaches 90%, which meets the carbon fiber standard.
  • This comparative example is the same as Example 1, except that the spinning tube in Step 1 does not have a splitter grid.
  • the strength of the fiber in Comparative Example 1 is only 2.3GPa, the modulus is 190GPa, and the elongation at break is only 1.2%, as shown in FIG. 3 .
  • This comparative example is the same as Example 1, and the difference is that the spinning solution in step 1 is a 10mg/g DMF phase spinning solution prepared by graphene oxide with an average sheet diameter of 30 microns.
  • the strength of the 2 fibers in the comparative example is only 2.5GPa, the modulus is 105GPa, and the elongation at break is 2.4%, as shown in FIG. 3 .
  • Graphene oxide with an average sheet diameter of 100 microns is formulated into an aqueous spinning solution of 8 mg/g, and is extruded into an aqueous solution (5%) of calcium chloride coagulation bath through a circular spinning tube with a diameter of 100 ⁇ m, passed through Nascent graphene oxide fibers are obtained by wet liquid crystal spinning; in this embodiment, a shunt grid is set in the circular spinning tube, and the liquid crystal spinning solution is divided into many microfiber structures through the device of the shunt grid.
  • the grid shape of the shunt grid is square, and the single hole size is 10 microns.
  • the nascent graphene oxide fiber is continuously drawn into the stretching bath prepared by acetic acid and water according to the volume ratio of 5:1, 3:1, and 1:1 for continuous three-stage stretching, and the total stretching ratio is 55%. %. .
  • plasticization increases the interlayer spacing of graphene oxide to 1.2-1.4 nm.
  • the fiber is continuously passed through a reduction bath prepared by hydroiodic acid and trifluoroacetic acid in a volume ratio of 1:6.
  • the temperature of the reduction bath is 25 degrees, and the fiber is subjected to tensile stress for 5 minutes. chemical reduction.
  • Example 2 After mechanical testing, the strength of the fiber in Example 2 reaches 4.3 GPa, the elongation at break is 3.1%, and the electrical conductivity is 1.25*10 4 S/m, as shown in FIG. 4 .
  • This comparative example is the same as Example 2, and the difference is that the reduction bath in step 4 is a reduction bath prepared by hydroiodic acid and ethanol at a volume ratio of 1:3, and the reduction is carried out for 12 hours at 25 degrees.
  • the reduction bath in step 4 is a reduction bath prepared by hydroiodic acid and ethanol at a volume ratio of 1:3, and the reduction is carried out for 12 hours at 25 degrees.
  • This comparative example is the same as Example 2, the difference is that the reduction bath in step 4 is heated to 50 degrees, after 2 minutes of reduction.
  • the strength of the fiber in Comparative Example 4 was 4 GPa, the elongation at break was 3%, and the electrical conductivity was 1.28*10 4 S/m, as shown in FIG. 4 .

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Abstract

本发明公开了一种室温下制备石墨烯基碳纤维的方法，所述纤维具有高强度、高模量、高韧性、高导电、高导热的优异特性。该方法如下：在喷丝头中嵌入流体液晶分区化的装置，氧化石墨烯纺丝液经分区化调控后，被划分成细小的微纤结构，进入凝固浴。对凝固后的氧化石墨烯纤维进行多级塑化拉伸，直至极限。紧接在张应力下将拉伸后的纤维通过配制好的高效还原浴进行还原。在室温下组装得到高强度、高模量、高韧性、高导电、高导热的石墨烯基碳纤维。本发明是一种在室温下制备石墨烯基碳纤维的方法，以氧化石墨烯代替聚合物作为碳纤维的前躯体，制备效率高，无需热处理，成本极低，节能环保。

Description

一种室温下制备石墨烯基碳纤维的方法 技术领域
本发明涉及纳米材料领域，特别是一种在室温下以二维氧化石墨烯为前驱体制备石墨烯基碳纤维的方法。
背景技术
传统碳纤维历经数十年的积累，已经发展出了许多高性能的纤维品种。然而，受限于分子融合碳化制备原理，碳纤维的制备必须经过复杂的高温热处理，才能形成完整的碳质结构。典型的聚丙烯腈碳纤维和沥青基碳纤维，在室温范围内作为一种有机物组成的纤维，完全不具备导电性，力学性能也很差，不具备实际应用价值。当热处理温度升高至600-800摄氏度时，有机物逐渐碳化形成一定的碳结构，传统碳纤维才逐步表现出了一定的导电性，强度逐渐提高。热处理温度继续升高至1000-2800摄氏度的温度范围时，碳结构逐步生长直至完善，其导电性和力学性能逐渐满足具体应用的需要。如此复杂的热处理过程伴随着巨大的能源消耗和环境污染。
2004年，英国曼彻斯特大学A.K.Geim教授课题组运用机械剥离法成功制备石墨烯。石墨烯具有超高的力学性能，模量达1100GPa，强度达130GPa；并且具有超高的热导率，达5000W/(m·K)；超高的电导率，达10 8S/m，以及超高的电流负载能力。集成如此多的性能优势使石墨烯成为单晶石墨晶须理想的构筑基元。2011年浙江大学高超课题组发明了一种以单层石墨烯为组装单元的宏观石墨烯纤维，开创了以天然石墨为原料制备碳质纤维的新路径。
目前来看，基于液晶湿法纺丝由氧化石墨烯制备石墨烯纤维的方法已慢慢发展成熟。相比传统碳纤维，石墨烯纤维具备优异的功能性，导电性和导热性都有明显的优势。2020年高超课题组再次报道了一种高性能石墨烯纤维，其电导率达到了10 6S/m，热导率达到了1580W/(m·K)，但是强度仅3GPa，与高强度的碳纤维仍有较大差距。同时，将前驱体氧化石墨烯纤维还原为纯碳质石墨烯纤维同样需要较为复杂的处理工艺，包括化学还原和1000-2800度的高温热处理，工艺繁琐，成本高昂。
基于节能环保、绿色发展的追求，本申请旨在有效提升氧化石墨烯纤维强度的同时，对其进行更高效清洁地还原处理。作为一种新型前驱体，氧化石墨烯本身就呈二维结构，且具有较高的含碳量和碳结构占比，理论上具有较低的还原活化能，因而更容易还原得到高质量的碳结构纤维。相较于传统碳纤维，从氧化石墨烯制备碳纤维有望在更低的能量条件下实现。
发明内容
为了克服上述传统碳纤维的技术缺陷，本发明旨在提供一种在室温下制备石墨烯基碳纤维的方法。经过简单化学还原后的石墨烯纤维，含碳量达到90％以上，符合碳纤维的标准，且具备媲美传统碳纤维的力学性能和更好的导热性能。
本发明针对氧化石墨烯这种二维平面大分子，其巨大的宽厚比使其具有良好的溶致液晶现象，巨大的分子又使其液晶的动力学稳定性良好，从而可以进行微纤化结构设计。具体的，本发明通过设置分区化流道来获得微纤化的氧化石墨烯纤维。具有液晶态的氧化石墨烯纺丝液被纺丝管前端的分流格栅切割成众多微纤化结构，并在纺丝管中保持微纤化结构。这种微纤化结构经过后续塑化拉伸后继续保留，同时拉伸使其取向度大大提升。更规则的取向和更致密的结构有利于在进一步化学还原后得到高性能的纤维，从而达到碳纤维的标准。更为重要的是，这种微纤化结构使得这种室温制备的石墨烯基碳纤维表现出兼具高强度和高韧性的性能。
本发明采用以下技术方案：
(1)将氧化石墨烯纺丝液挤入分区化流道，所述分区化流道包括纺丝管以及垂直设置于纺丝管前段的分流格栅；氧化石墨烯纺丝液经过分流格栅被切割成众多微纤化结构，并在纺丝管后段保持微纤化结构；
(2)将步骤1获得的微纤化结构的氧化石墨烯液晶先进挤入凝固浴，得到初生的微纤化氧化石墨烯纤维。随后牵引入拉伸浴中，浸泡使其塑化，塑化使得氧化石墨烯的层间距增大，控制层间距在1.1-1.8nm，使塑性变形达到最佳效果。当层间距继续增加，由于层间相互作用太弱，导致氧化石墨烯层之间发生滑移，宏观纤维很容易断裂。
(3)在拉伸浴中对塑化后的纤维进行连续多级拉伸，总拉伸率为50％，保持外力，以保持氧化石墨烯片层的平直排列，释放掉片层间的应力；
(4)接着将纤维连续通过还原浴，调整还原浴前后送丝机转速比使得拉伸倍数大于1，使纤维在张应力下进行快速的化学还原；
(5)最后将还原后的石墨烯纤维进行定型处理，得到室温下组装制备的高性能石墨烯基碳纤维。
进一步地，步骤1所述纺丝管形状为圆形；分流格栅的栅格形状包括且不限于圆形，方形，三角形，六边形及各种复杂形状。
进一步地，步骤1所述的纺丝液为氧化石墨烯的水相分散液、DMF相分散液、DMAc 相分散液、DMSO相分散液。
进一步地，步骤2所述的凝固浴为乙酸乙酯、二氯甲烷、乙酸、乙醇、水、异丙醇、三氯甲烷、丙酮等及其混合凝固浴。
进一步地，步骤2所述拉伸浴为乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺等或其混合溶剂。
进一步地，步骤3所述多级拉伸要进行3次以上。
进一步地，步骤4所述化学还原所采用的试剂为氢碘酸与乙醇、乙酸、氟乙酸、二氟乙酸、三氟乙酸、氯乙酸、二氯乙酸、三氯乙酸、溴乙酸、二溴乙酸、三溴乙酸、碘乙酸、二碘乙酸、三碘乙酸的混合溶液，或者水合肼、抗坏血酸钠、氯化亚锡等。
本发明的有益效果在于：本发明借助氧化石墨烯作为碳纤维的前驱体，基于湿法液晶纺丝的方法，以分区化流道调控纤维结构，通过1～50％的塑性加工区间，配以连续在化学还原浴中的拉伸，在室温下经过充分高效的化学还原便能制备出性能优异的石墨烯基碳纤维。还原后含碳量达到90％以上，相比高强型PAN基碳纤维，强度可达到5.5GPa，模量240GPa，韧性75MJ/m 3，强度与T800系列高强型碳纤维媲美，且具有更好的韧性；热导率达到230W/(m·K)，有明显优势；电导率1.3*10 4S/m，与之相近。尤其是相对传统碳纤维所必须的高温热处理，本发明的石墨烯基碳纤维全程无需热处理，绿色环保，大大降低成本的同时实现了高性能，是一种兼具高强度、高模量、高韧性、高导电、高导热新型石墨烯基碳纤维材料。
附图说明
图1为本发明的增强流程图。
图2为纺丝管内氧化石墨烯液晶冻干后的微纤化结构特征。
图3为3种石墨烯纤维和T-800碳纤维的典型力学曲线，Control为未微纤化的纤维；GF-100和GF-30分别为100微米和30微米氧化石墨烯原料制备的微纤化结构的石墨烯纤维。
图4为不同还原条件下还原时纤维电导率的原位测试结果。
具体实施方式
实施例1
(1)将平均片径100微米的氧化石墨烯配制成8mg/g的DMF相纺丝液，经直径 为100μm的圆形纺丝管挤入乙酸乙酯凝固浴，通过湿法液晶纺丝得到初生的氧化石墨烯纤维；本实施例中，圆形纺丝管中设置分流格栅，液晶纺丝液经过分流格栅的装置被分割成众多微纤结构。分流格栅的栅格形状为正方形，单孔尺寸为10微米。
(2)将初生的氧化石墨烯纤维，连续牵引入乙酸和水按照体积比5:1、3:1、1:1配制的拉伸浴中进行连续3级拉伸，总拉伸率为50％。在每道拉伸浴中，塑化使得氧化石墨烯的层间距增大至1.2-1.4nm。
(3)接着以3％的正拉伸率将纤维连续通氢碘酸与三氟乙酸按体积比1:6配制的还原浴，还原浴温度为25度，使纤维在张应力下进行5分钟的化学还原。
(4)最后将充分还原后的石墨烯纤维进行定型处理，得到室温下组装制备的高性能石墨烯基碳纤维。
经过力学、热导率、电导率测试，实施例1中室温制备的石墨烯基碳纤维强度可达到5.5GPa，模量240GPa，断裂伸长率为2.3％，韧性75MJ/m 3，如图3所示；热导率达到230W/(m·K)；电导率1.3*10 4S/m。且碳含量达到90％，符合碳纤维标准。
对比例1
本对比例同实施例1，区别在于，步骤1中的纺丝管不具有分流格栅。
经过测试，对比例1中纤维的强度只有2.3GPa，模量190GPa，断裂伸长率仅为1.2％，如图3所示。
对比例2
本对比例同实施例1，区别在于，步骤1中的纺丝液为平均片径30微米的氧化石墨烯配制的10mg/g DMF相纺丝液。
经过测试，对比例中2纤维的强度只有2.5GPa，模量105GPa，断裂伸长率为2.4％，如图3所示。
实施例2
(1)将平均片径100微米的氧化石墨烯配制成8mg/g的水相纺丝液，经直径为100μm的圆形纺丝管挤入氯化钙的水溶液(5％)凝固浴，通过湿法液晶纺丝得到初生的氧化石墨烯纤维；本实施例中，圆形纺丝管中设置分流格栅，液晶纺丝液经过分流格栅的装置被分割成众多微纤结构。分流格栅的栅格形状为正方形，单孔尺寸为10微米。
(2)将初生的氧化石墨烯纤维，连续牵引入乙酸和水按照体积比5:1、3:1、1:1配制的拉伸浴中进行连续3级拉伸，总拉伸率为55％。。在每道拉伸浴中，塑化使得 氧化石墨烯的层间距增大至1.2-1.4nm。
(3)接着以2％的正拉伸率将纤维连续通氢碘酸与三氟乙酸按体积比1:6配制的还原浴，还原浴温度为25度，使纤维在张应力下进行5分钟的化学还原。
(4)最后将充分还原后的石墨烯纤维进行定型处理，得到室温下组装制备的高性能石墨烯基碳纤维。
经过力学测试，实施例2中纤维强度达4.3GPa，断裂伸长率为3.1％，电导率1.25*10 4S/m，如图4所示。
对比例3
本对比例同实施例2，区别在于，步骤4中的还原浴为氢碘酸与乙醇按体积比1:3配制的还原浴，在25度下经过12小时的还原。
经过测试，对比例3中纤维的强度为4.2GPa，断裂伸长率为2.8％，电导率1.26*10 4S/m，如图4所示。
对比例4
本对比例同实施例2，区别在于，步骤4中的还原浴被加热到50度，经过2分钟的还原。
经过测试，对比例4中纤维的强度为4GPa，断裂伸长率为3％，电导率1.28*10 4S/m，如图4所示。

Claims (4)

  1. 一种室温下制备石墨烯基碳纤维的方法，其特征在于，包括如下过程：
    (1)将氧化石墨烯纺丝液挤入分区化流道，所述分区化流道包括纺丝管以及垂直设置于纺丝管前段的分流格栅；氧化石墨烯纺丝液经过分流格栅被切割成众多微纤化结构，并在纺丝管后段保持微纤化结构；
    (2)将步骤1获得的微纤化结构的氧化石墨烯液晶先进挤入凝固浴，得到初生的微纤化氧化石墨烯纤维。随后牵引入拉伸浴中，浸泡使其塑化，塑化使得氧化石墨烯的层间距增大；所述拉伸浴为乙醇、丙酮、异丙醇、乙酸、乙酸乙酯、甲醇、水、丙三醇、丙二醇、乙二醇、三乙二醇、四乙二醇、五乙二醇、盐酸、有机胺等或其混合溶剂；
    (3)在拉伸浴中对塑化后的纤维进行连续多级拉伸，总拉伸率为50％，保持外力，以保持氧化石墨烯片层的平直排列，释放掉片层间的应力；
    (4)接着将纤维连续通过还原浴，在拉伸状态下进行化学还原；
    (5)最后将充分还原后的石墨烯纤维进行定型处理，施加外力以保持当前长度，得到室温下组装制备的高性能石墨烯基碳纤维。
  2. 根据权利要求1所述的制备方法，其特征在于，所述纺丝管形状为圆形、方形或各种复杂不规则形状；分流格栅的栅格形状包括且不限于圆形，方形，三角形，六边形及各种复杂形状。
  3. 根据权利要求1所述的制备方法，其特征在于，所述的纺丝液为氧化石墨烯的水相分散液、DMF相分散液、DMAc相分散液、DMSO相分散液，凝固浴为乙酸乙酯、二氯甲烷、乙酸、乙醇、水、异丙醇、三氯甲烷、丙酮等及其混合凝固浴。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(4)中，化学还原所采用的试剂为氢碘酸与乙醇、乙酸、氟乙酸、二氟乙酸、三氟乙酸、氯乙酸、二氯乙酸、三氯乙酸、溴乙酸、二溴乙酸、三溴乙酸、碘乙酸、二碘乙酸、三碘乙酸的混合溶液或者水合肼、抗坏血酸钠、氯化亚锡等。
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