CN103086367A - Preparation method of polylactic acid functionalized graphene - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004626 polylactic acid Substances 0.000 title abstract description 39
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 20
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
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- 230000010355 oscillation Effects 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims 1
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- 239000003999 initiator Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
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- 238000002411 thermogravimetry Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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Abstract
一种聚乳酸功能化石墨烯的制备方法。其是先通过改进的Hummers方法制备氧化石墨，超声剥离，冷冻干燥制备氧化石墨烯；然后将氧化石墨烯与无水乳酸以一定比例混合，加入催化剂，在真空环境下原位聚合，制备石墨烯/聚乳酸复合物；最后洗去未与石墨烯共价结合的聚乳酸，得到聚乳酸功能化的石墨烯。本发明提供的聚乳酸功能化石墨烯的制备方法是以氧化石墨烯作为引发剂，通过乳酸缩聚，一步法将聚乳酸接枝到氧化石墨烯的表面。该方法无需对石墨烯进行预处理，乳酸缩聚处理过程相对简单，容易实现，且成本较低。此外，氧化石墨烯表面羧基、羟基等含氧官能团丰富，经过简单的处理，即可得到较高的接枝率。
A preparation method of polylactic acid functionalized graphene. It first prepares graphite oxide by the improved Hummers method, ultrasonically exfoliates, and freeze-dries to prepare graphene oxide; then mixes graphene oxide and anhydrous lactic acid in a certain proportion, adds a catalyst, and in-situ polymerizes in a vacuum environment to prepare graphene /polylactic acid complex; finally wash away the polylactic acid that is not covalently bonded to the graphene to obtain polylactic acid functionalized graphene. The preparation method of the polylactic acid functionalized graphene provided by the invention uses graphene oxide as an initiator to graft polylactic acid onto the surface of the graphene oxide through polycondensation of lactic acid in one step. This method does not require pretreatment of graphene, and the lactic acid polycondensation process is relatively simple, easy to implement, and low in cost. In addition, the surface of graphene oxide is rich in oxygen-containing functional groups such as carboxyl groups and hydroxyl groups, and a high grafting rate can be obtained after simple treatment.
Description
技术领域technical field
本发明属于碳纳米材料改性技术领域，特别是涉及一种以氧化石墨烯(GO)为引发剂，通过乳酸缩聚，一步法制备聚乳酸功能化石墨烯(GO-g-PLA)的方法。The invention belongs to the technical field of modification of carbon nanomaterials, and in particular relates to a method for preparing polylactic acid functionalized graphene (GO-g-PLA) in one step by using graphene oxide (GO) as an initiator through polycondensation of lactic acid.
背景技术Background technique
聚乳酸是可生物降解聚合物中的典型代表，属于聚α羟基酸衍生物，具有较好的力学性能、生物相容性和可降解性，但韧性差、强度低等缺点限制了它的广泛应用。石墨烯自2004年被发现以来，以其优异的力学性能、超高的比表面和表面丰富的官能团等特征，已在聚合物增强、增韧方面显示出巨大的潜能。研究表明，添加少量的石墨烯就能在聚合物基体中形成交叉的网络结构，有效地提高材料的各方面性能，因此利用聚乳酸改性石墨烯受到了格外的关注和重视，目前已成为新型材料领域研发的重点和热点。但是由于石墨烯具有较大的比表面积和表面自由能，在分子间作用力的相互作用下，很容易形成尺寸较大的团聚体，而且石墨烯是单一碳原子通过sp3和sp2杂化组成的，化学活性低，与聚乳酸基体复合时很难形成牢固稳定的界面结合。因此，当以石墨烯作为增强材料制备复合材料时，石墨烯首先要经过表面改性，以降低表面能，减少团聚，提高分散性；并改善其与基体之间的润湿性，提高界面结合强度。Polylactic acid is a typical representative of biodegradable polymers. It belongs to poly-alpha hydroxy acid derivatives. It has good mechanical properties, biocompatibility and degradability, but its shortcomings such as poor toughness and low strength limit its wide application. application. Since its discovery in 2004, graphene has shown great potential in polymer reinforcement and toughening due to its excellent mechanical properties, ultra-high specific surface area and abundant functional groups on the surface. Studies have shown that adding a small amount of graphene can form a cross network structure in the polymer matrix, which can effectively improve the performance of the material in all aspects. Therefore, the use of polylactic acid modified graphene has received special attention and attention. It has become a new type of Key points and hotspots of research and development in the field of materials. However, due to the large specific surface area and surface free energy of graphene, it is easy to form large aggregates under the interaction of intermolecular forces, and graphene is a single carbon atom hybridized by sp 3 and sp 2 Composition, low chemical activity, it is difficult to form a firm and stable interfacial bond when compounded with polylactic acid matrix. Therefore, when graphene is used as a reinforcing material to prepare composite materials, graphene must first undergo surface modification to reduce surface energy, reduce agglomeration, and improve dispersibility; and improve the wettability between it and the matrix to improve interfacial bonding. strength.
目前各国的研究人员在石墨烯功能化方面做了大量研究，也取得了一系列的成果，但在如何简捷、高效地对石墨烯进行改性，使其与基体有更好的相容性方面仍然存在一些问题，寻找高效、快捷的石墨烯改性方法对于石墨烯的广泛应用具有积极的促进作用。At present, researchers from various countries have done a lot of research on the functionalization of graphene and achieved a series of results, but in terms of how to modify graphene simply and efficiently so that it has better compatibility with the matrix There are still some problems, and finding efficient and fast graphene modification methods will play a positive role in promoting the wide application of graphene.
发明内容Contents of the invention
为了解决上述问题，本发明的目的在于提供一种可有效提高石墨烯在有机溶剂中的分散性，并增强其与聚乳酸基体的界面结合强度的聚乳酸功能化石墨烯的制备方法。In order to solve the above problems, the object of the present invention is to provide a method for preparing polylactic acid functionalized graphene that can effectively improve the dispersibility of graphene in organic solvents and enhance the interfacial bonding strength between it and polylactic acid matrix.
为了达到上述目的，本发明提供的聚乳酸功能化石墨烯的制备方法包括按顺序进行的下列步骤：In order to achieve the above object, the preparation method of polylactic acid functionalized graphene provided by the invention comprises the following steps carried out in order:
1)采用改进的Hummers方法将石墨制备成氧化石墨，然后将氧化石墨洗涤干燥后溶解在去离子水中，之后超声振荡而将氧化石墨剥离，最后经干燥得到粉末状氧化石墨烯；1) Using the improved Hummers method to prepare graphite into graphite oxide, then washing and drying the graphite oxide and dissolving it in deionized water, then ultrasonically vibrating to peel off the graphite oxide, and finally drying to obtain powdered graphene oxide;
2)将乳酸置于反应器皿中，然后置于油浴锅中减压蒸馏，得到无水乳酸；2) Lactic acid is placed in a reaction vessel, and then placed in an oil bath for distillation under reduced pressure to obtain anhydrous lactic acid;
3)将上述无水乳酸与氧化石墨烯以20∶1～320∶1的质量比混合，升温至160℃～190℃，加入催化剂，在≤100Pa的真空度下熔融缩聚，反应结束后进行冷却，之后用三氯甲烷反复溶解，以洗去未与石墨烯共价结合的聚乳酸，最终得到所述的聚乳酸功能化石墨烯(GO-g-PLA)。3) Mix the above-mentioned anhydrous lactic acid and graphene oxide at a mass ratio of 20:1 to 320:1, heat up to 160°C to 190°C, add a catalyst, melt and polycondense under a vacuum of ≤100Pa, and cool down after the reaction , and then repeatedly dissolved with chloroform to wash away the polylactic acid that is not covalently bonded to the graphene, and finally obtain the polylactic acid functionalized graphene (GO-g-PLA).
所述的步骤1)中氧化石墨在去离子水中的溶解浓度为1mg/ml～3mg/ml，超声振荡的功率为100w～1000w，超声振荡时间为2h～5h，干燥温度为-60℃～80℃。In the step 1), the dissolved concentration of graphite oxide in deionized water is 1 mg/ml to 3 mg/ml, the power of ultrasonic oscillation is 100w to 1000w, the time of ultrasonic oscillation is 2h to 5h, and the drying temperature is -60°C to 80°C. ℃.
所述的步骤2)中油浴的温度为90℃～120℃，减压蒸馏时间为2h～5h。The temperature of the oil bath in the step 2) is 90°C-120°C, and the vacuum distillation time is 2h-5h.
所述的步骤3)中催化剂为辛酸亚锡或氯化亚锡，无水乳酸与催化剂的质量比为1000∶1～50∶1，熔融缩聚时间为5h～24h。The catalyst in the step 3) is stannous octoate or stannous chloride, the mass ratio of anhydrous lactic acid to the catalyst is 1000:1-50:1, and the melt polycondensation time is 5h-24h.
本发明提供的聚乳酸功能化石墨烯的制备方法是以氧化石墨烯作为引发剂，通过乳酸缩聚，一步法将聚乳酸接枝到氧化石墨烯的表面。该方法无需对石墨烯进行预处理，乳酸缩聚处理过程相对简单，容易实现，且成本较低。此外，氧化石墨烯表面羧基、羟基等含氧官能团丰富，经过简单的处理，即可得到较高的接枝率。The preparation method of the polylactic acid functionalized graphene provided by the invention uses graphene oxide as an initiator to graft polylactic acid onto the surface of the graphene oxide through polycondensation of lactic acid in one step. This method does not require pretreatment of graphene, and the lactic acid polycondensation process is relatively simple, easy to implement, and low in cost. In addition, the surface of graphene oxide is rich in oxygen-containing functional groups such as carboxyl groups and hydroxyl groups, and a high grafting rate can be obtained after simple treatment.
附图说明Description of drawings
图1为本发明实施例1-3提供的GO-g-PLA热重分析(TG)图。Fig. 1 is the thermogravimetric analysis (TG) diagram of GO-g-PLA provided by Examples 1-3 of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施例对本发明提供的聚乳酸功能化石墨烯的制备方法进行详细说明。The preparation method of the polylactic acid functionalized graphene provided by the present invention will be described in detail below in conjunction with the accompanying drawings and specific examples.
实施例1：Example 1:
首先按照改进的Hummers方法将石墨制备成氧化石墨，具体方法是将21g质量比为1∶6的鳞片石墨/高锰酸钾混合固体缓慢加入到体积比为9∶1的400mL H2SO4/H3PO4混合溶液中，待混合均匀后，放置在50℃恒温水浴锅中持续搅拌12h，之后倒入H2O2冰浴中，静置24h，然后用去离子水反复离心洗涤至中性，之后在45℃的温度下真空干燥而得到氧化石墨。将上述氧化石墨配置成1mg/ml的氧化石墨水溶液，然后在常温下超声振荡2.5h而将氧化石墨剥离，最后在-50℃的温度下冷冻干燥而得到粉末状氧化石墨烯。Firstly, graphite was prepared into graphite oxide according to the modified Hummers method. The specific method was to slowly add 21 g of flake graphite/potassium permanganate mixed solid with a mass ratio of 1:6 to 400 mL of H 2 SO 4 / In the H 3 PO 4 mixed solution, after mixing evenly, place it in a 50°C constant temperature water bath and continue to stir for 12 hours, then pour it into an H 2 O 2 ice bath, let it stand for 24 hours, and then use deionized water to repeatedly centrifuge and wash to medium properties, and then vacuum-dried at a temperature of 45° C. to obtain graphite oxide. The above-mentioned graphite oxide was prepared into a 1 mg/ml graphite oxide aqueous solution, then ultrasonically oscillated at room temperature for 2.5 hours to peel off the graphite oxide, and finally freeze-dried at a temperature of -50° C. to obtain powdered graphene oxide.
之后在250ml反应瓶中加入120ml乳酸，然后置于100℃的油浴锅中，在300Pa的真空度下减压蒸馏脱水3h，得到无水乳酸。Then add 120ml of lactic acid into a 250ml reaction bottle, then place it in an oil bath at 100°C, and dehydrate under a vacuum of 300Pa for 3 hours to obtain anhydrous lactic acid.
然后在上述反应瓶中加入0.3g粉末状氧化石墨烯和0.5g作为催化剂的辛酸亚锡，超声处理5min，之后在180℃的温度，70Pa的真空度下熔融缩聚5h。将反应液冷却，然后用三氯甲烷反复溶解，以洗去未与石墨烯共价结合的聚乳酸，最后在50℃的温度下真空干燥24h，得到GO-g-PLA。Then, 0.3 g of powdered graphene oxide and 0.5 g of stannous octoate as a catalyst were added into the above-mentioned reaction flask, ultrasonically treated for 5 min, and then melted and polycondensed at a temperature of 180° C. and a vacuum of 70 Pa for 5 h. The reaction liquid was cooled, and then repeatedly dissolved with chloroform to wash away the polylactic acid not covalently bonded to graphene, and finally vacuum-dried at 50 °C for 24 h to obtain GO-g-PLA.
实施例2：Example 2:
按实施例1的方法制备氧化石墨烯。Graphene oxide was prepared by the method of Example 1.
之后在250ml反应瓶中加入120ml乳酸，然后置于100℃的油浴锅中，在300Pa的真空度下减压蒸馏脱水4h，得到无水乳酸。Then add 120ml of lactic acid into a 250ml reaction bottle, then place it in an oil bath at 100°C, and conduct vacuum distillation and dehydration under a vacuum of 300Pa for 4 hours to obtain anhydrous lactic acid.
然后在上述反应瓶中加入0.5g粉末状氧化石墨烯和0.3g作为催化剂的氯化亚锡，超声处理5min，之后在170℃的温度，70Pa的真空度下熔融缩聚8h。将反应液冷却，然后用三氯甲烷反复溶解，以洗去未与石墨烯共价结合的聚乳酸，最后在50℃的温度下真空干燥24h，得到GO-g-PLA。Then, 0.5 g of powdered graphene oxide and 0.3 g of stannous chloride as a catalyst were added to the above reaction flask, ultrasonically treated for 5 min, and then melted and polycondensed at a temperature of 170° C. and a vacuum of 70 Pa for 8 h. The reaction liquid was cooled, and then repeatedly dissolved with chloroform to wash away the polylactic acid not covalently bonded to graphene, and finally vacuum-dried at 50 °C for 24 h to obtain GO-g-PLA.
实施例3：Example 3:
按实施例1的方法制备氧化石墨烯。Graphene oxide was prepared by the method of Example 1.
之后在250ml反应瓶中加入120ml乳酸，然后置于100℃的油浴锅中，在300Pa的真空度下减压蒸馏脱水4h，得到无水乳酸。Then add 120ml of lactic acid into a 250ml reaction bottle, then place it in an oil bath at 100°C, and conduct vacuum distillation and dehydration under a vacuum of 300Pa for 4 hours to obtain anhydrous lactic acid.
然后在上述反应瓶中加入0.8g粉末状氧化石墨烯和0.3g作为催化剂的辛酸亚锡，超声处理5min，之后在170℃的温度，70Pa的真空度下熔融缩聚12h。将反应液冷却，用三氯甲烷反复溶解，以洗去未与石墨烯共价结合的聚乳酸，最后在50℃的温度下真空干燥24h，得到GO-g-PLA。Then, 0.8 g of powdered graphene oxide and 0.3 g of stannous octoate as a catalyst were added to the above reaction flask, ultrasonically treated for 5 min, and then melted and polycondensed at a temperature of 170° C. and a vacuum of 70 Pa for 12 h. The reaction solution was cooled and dissolved repeatedly with chloroform to wash away polylactic acid not covalently bonded to graphene, and finally dried in vacuum at 50°C for 24 hours to obtain GO-g-PLA.
本发明人对由上述实施例制备出的GO-g-PLA在30℃～700℃的温度，氮气保护下进行了热重分析试验，热重分析(TG)图如图1所示，其中右侧从下至下的三条曲线分别应对于实施例3、实施例1和实施例2制备出的GO-g-PLA，从图中可以看出，实施例1制备出的GO-g-PLA在320℃左右聚乳酸将分解，故GO-g-PLA的接枝率为25％左右。实施例2制备出的GO-g-PLA在320℃左右聚乳酸将分解，故GO-g-PLA的接枝率为30％左右。实施例3制备出的GO-g-PLA在320℃左右聚乳酸将分解，故GO-g-PLA的接枝率为20％左右。The present inventor has carried out thermogravimetric analysis test on GO-g-PLA prepared by the above examples at a temperature of 30°C to 700°C under the protection of nitrogen. The thermogravimetric analysis (TG) diagram is shown in Figure 1, where the right The three curves from bottom to bottom correspond to the GO-g-PLA prepared in Example 3, Example 1 and Example 2 respectively. It can be seen from the figure that the GO-g-PLA prepared in Example 1 is in Polylactic acid will decompose at about 320°C, so the grafting rate of GO-g-PLA is about 25%. The GO-g-PLA prepared in Example 2 will decompose polylactic acid at about 320°C, so the grafting rate of GO-g-PLA is about 30%. The GO-g-PLA prepared in Example 3 will decompose polylactic acid at about 320°C, so the grafting rate of GO-g-PLA is about 20%.
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| CN103804661A (en) * | 2014-01-22 | 2014-05-21 | 盐城菁华新材料科技有限公司 | Graphene/polylactic acid composite material and preparation method thereof |
| CN105754310A (en) * | 2016-03-30 | 2016-07-13 | 成都新柯力化工科技有限公司 | Graphene nanoplatelet master batch for enhancing bioplastics and preparation method |
| CN106317387A (en) * | 2016-08-29 | 2017-01-11 | 佛山市高明区尚润盈科技有限公司 | Preparation method of electrostatic prevention and antibiotic polylactic acid material |
| CN106589461A (en) * | 2016-12-22 | 2017-04-26 | 西安理工大学 | Preparation method of triglycidyl isocyanurate/graphene oxide composite material |
| CN106957417A (en) * | 2017-03-27 | 2017-07-18 | 中国地质大学（武汉） | A kind of method that galapectite graphene oxide complex catalysts prepare poly epsilon caprolactone lactone |
| CN107216462A (en) * | 2017-06-09 | 2017-09-29 | 大连大学 | A kind of preparation method of carboxylated graphene oxide surface grafting polylactic acid composition |
| CN108394897A (en) * | 2018-05-25 | 2018-08-14 | 清华-伯克利深圳学院筹备办公室 | A kind of magnanimity preparation method of porous oxidation graphene |
| US10160857B2 (en) | 2014-11-05 | 2018-12-25 | Samsung Electronics Co., Ltd. | Thermoplastic resin composition and molded article made therefrom |
| CN111187496A (en) * | 2020-02-12 | 2020-05-22 | 东华大学 | Preparation method and application of multifunctional bio-based degradable polylactic resin |
| CN112094421A (en) * | 2020-08-20 | 2020-12-18 | 湖北中烟工业有限责任公司 | A kind of modified reduced graphene oxide doped polylactic acid film and preparation method thereof |
| CN113402758A (en) * | 2021-06-17 | 2021-09-17 | 江苏尚美医疗器械有限公司 | Degradable shape memory medical splint and processing technology thereof |
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| CN114437318A (en) * | 2022-03-09 | 2022-05-06 | 深圳石墨烯创新中心有限公司 | A kind of preparation method of graphene oxide-polylactic acid composite material |
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| CN103804661B (en) * | 2014-01-22 | 2016-03-23 | 成都电科华清科技有限责任公司 | A kind of graphene/polylactic acid composite material and preparation method thereof |
| CN103804661A (en) * | 2014-01-22 | 2014-05-21 | 盐城菁华新材料科技有限公司 | Graphene/polylactic acid composite material and preparation method thereof |
| US10160857B2 (en) | 2014-11-05 | 2018-12-25 | Samsung Electronics Co., Ltd. | Thermoplastic resin composition and molded article made therefrom |
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| CN106957417B (en) * | 2017-03-27 | 2019-03-19 | 中国地质大学（武汉） | A kind of method that galapectite graphene oxide complex catalysts prepare poly-epsilon-caprolactone |
| CN106957417A (en) * | 2017-03-27 | 2017-07-18 | 中国地质大学（武汉） | A kind of method that galapectite graphene oxide complex catalysts prepare poly epsilon caprolactone lactone |
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| CN108394897A (en) * | 2018-05-25 | 2018-08-14 | 清华-伯克利深圳学院筹备办公室 | A kind of magnanimity preparation method of porous oxidation graphene |
| CN111187496A (en) * | 2020-02-12 | 2020-05-22 | 东华大学 | Preparation method and application of multifunctional bio-based degradable polylactic resin |
| CN111187496B (en) * | 2020-02-12 | 2021-09-10 | 东华大学 | Preparation method and application of multifunctional bio-based degradable polylactic resin |
| CN112094421A (en) * | 2020-08-20 | 2020-12-18 | 湖北中烟工业有限责任公司 | A kind of modified reduced graphene oxide doped polylactic acid film and preparation method thereof |
| CN112094421B (en) * | 2020-08-20 | 2022-12-27 | 湖北中烟工业有限责任公司 | Preparation method of modified reduced graphene oxide doped polylactic acid film |
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