CN103086367A - Preparation method of polylactic acid functionalized graphene - Google Patents

Preparation method of polylactic acid functionalized graphene Download PDF

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Publication number
CN103086367A
CN103086367A CN2013100147355A CN201310014735A CN103086367A CN 103086367 A CN103086367 A CN 103086367A CN 2013100147355 A CN2013100147355 A CN 2013100147355A CN 201310014735 A CN201310014735 A CN 201310014735A CN 103086367 A CN103086367 A CN 103086367A
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lactic acid
graphene
preparation
poly
polylactic acid
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徐志伟
李文肖
岳梦瑶
单明景
郭启微
买巍
杨彩云
钱晓明
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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Abstract

The invention discloses a preparation method of polylactic acid functionalized graphene, which comprises the steps of preparing graphite oxide by adopting an improved Hummers method; performing ultrasonic peeling and freeze drying to obtain graphene oxide; mixing the graphene oxide with anhydrous lactic acid at certain proportion; adding a catalyst, and performing in-situ polymerization in vacuum environment to obtain a graphene/polylactic acid complex; and washing off the polylactic acid not in covalent binding with graphene to obtain polylactic acid functionalized graphene. The preparation method of polylactic acid functionalized graphene provided by the invention takes graphene oxide as an initiator and grafts polylactic acid to the surface of graphene oxide through lactic acid condensation polymerization by adopting a one-step method. The method does not need to perform pretreatment on graphene; the treatment process of lactic acid condensation polymerization is relatively simple and easy to realize, and the cost is relatively low. Moreover, the surface of graphene oxide is rich in oxygen-containing functional groups such as carboxyl group, hydroxyl group and the like; and relatively high grafting rate can be obtained through simple treatment.

Description

A kind of preparation method of poly(lactic acid) functionalization graphene
Technical field
The invention belongs to carbon nanomaterial modification technology field, particularly relate to a kind ofly take graphene oxide (GO) as initiator, by the lactic acid polycondensation, single stage method prepares the method for poly(lactic acid) functionalization graphene (GO-g-PLA).
Background technology
Poly(lactic acid) is the Typical Representative in biodegradable polymers, belongs to poly-alpha-hydroxy acid derivative, has mechanical property, biocompatibility and degradability preferably, but the drawbacks limit such as poor toughness, intensity be low its widespread use.Graphene is since 2004 are found, with the abundant features such as functional group of the specific surface of its excellent mechanical property, superelevation and surface, at enhancing by polymer, demonstrate huge potential aspect toughness reinforcing.Studies show that, add a small amount of Graphene and just can form the network structure of intersecting in polymeric matrix, effectively improve the various aspects of performance of material, therefore utilize polylactic acid modified Graphene to be subject to concern and attention especially, become emphasis and the focus of field of novel research and development at present.But because Graphene has larger specific surface area and surface free energy, under the interaction of Intermolecular Forces, be easy to form larger-size coacervate, and Graphene is that single carbon atom passes through sp 3And sp 2Hydridization forms, and chemically reactive is low, is combined in the interface that is difficult to the formation firm stable when polylactic acid based volume recombination.Therefore, when preparing matrix material with Graphene as strongthener, at first Graphene will pass through surface modification, to fall low surface energy, reduces and reunites, and improves dispersed; And improve wettability between itself and matrix, improve interface bond strength.
The researchist of various countries has done large quantity research aspect graphene functionalized at present, also obtained a series of achievement, but simple and direct how, efficiently Graphene is carried out modification, make itself and matrix have better consistency aspect still to have some problems, seek efficiently, the Graphene method of modifying has positive promoter action for the widespread use of Graphene efficiently.
Summary of the invention
In order to address the above problem, to the object of the present invention is to provide and a kind ofly can effectively improve the dispersiveness of Graphene in organic solvent, and strengthen the preparation method of poly(lactic acid) functionalization graphene of the interface bond strength of itself and poly(lactic acid) matrix.
In order to achieve the above object, the preparation method of poly(lactic acid) functionalization graphene provided by the invention comprises the following step that carries out in order:
1) adopt improved Hummers method that graphite is prepared into graphite oxide, be dissolved in deionized water after then graphite oxide being washed drying, sonic oscillation and graphite oxide is peeled off, obtain Powdered graphene oxide finally by drying afterwards;
2) lactic acid is placed in reaction vessels, then is placed in the oil bath pan underpressure distillation, obtain anhydrous lactic acid;
3) above-mentioned anhydrous lactic acid is mixed with the mass ratio of graphene oxide with 20: 1~320: 1, be warming up to 160 ℃~190 ℃, add catalyzer, melt phase polycondensation under the vacuum tightness of≤100Pa, carry out cooling after reaction finishes, repeatedly dissolve with trichloromethane afterwards, to wash away not and the covalently bound poly(lactic acid) of Graphene, finally obtain described poly(lactic acid) functionalization graphene (GO-g-PLA).
Described step 1) in, the concentration of ordinary dissolution of graphite oxide in deionized water is 1mg/ml~3mg/ml, and the power of sonic oscillation is 100w~1000w, and the sonic oscillation time is 2h~5h, and drying temperature is-60 ℃~80 ℃.
Described step 2) in, the temperature of oil bath is 90 ℃~120 ℃, and the underpressure distillation time is 2h~5h.
Described step 3) in, catalyzer is stannous octoate or tin protochloride, and the mass ratio of anhydrous lactic acid and catalyzer is 1000: 1~50: 1, and the melt phase polycondensation time is 5h~24h.
The preparation method of poly(lactic acid) functionalization graphene provided by the invention be with graphene oxide as initiator, by the lactic acid polycondensation, single stage method is grafted to poly(lactic acid) on the surface of graphene oxide.The method need not Graphene is carried out pre-treatment, and lactic acid polycondensation treating processes is relatively simple, easily realize, and cost is lower.In addition, the oxygen-containing functional groups such as the surperficial carboxyl of graphene oxide, hydroxyl are abundant, through simply processing, can obtain higher percentage of grafting.
Description of drawings
GO-g-PLA thermogravimetric analysis (TG) figure that Fig. 1 provides for embodiment of the present invention 1-3.
Embodiment
Preparation method to poly(lactic acid) functionalization graphene provided by the invention is elaborated below in conjunction with the drawings and specific embodiments.
Embodiment 1:
At first according to improved Hummers method, graphite is prepared into graphite oxide, concrete grammar is to be that slowly to join volume ratio be the 400mL H of 9: 1 for the crystalline flake graphite/potassium permanganate blended solid of 1: 6 with the 21g mass ratio 2SO 4/ H 3PO 4In mixing solutions, to be mixed evenly after, be placed on and continue in 50 ℃ of thermostat water baths to stir 12h, pour afterwards H into 2O 2In ice bath, standing 24h, then with deionized water repeatedly centrifuge washing to neutral, vacuum-drying and obtain graphite oxide at the temperature of 45 ℃ afterwards.Above-mentioned graphite oxide is configured to the graphite oxide aqueous solution of 1mg/ml, sonic oscillation 2.5h and graphite oxide is peeled off at normal temperatures then, last lyophilize at the temperature of-50 ℃ and obtain Powdered graphene oxide.
Add afterwards 120ml lactic acid in the 250ml reaction flask, then be placed in the oil bath pan of 100 ℃, underpressure distillation dehydration 3h, obtain anhydrous lactic acid under the vacuum tightness of 300Pa.
Then add the Powdered graphene oxide of 0.3g and 0.5g as the stannous octoate of catalyzer in above-mentioned reaction flask, supersound process 5min, afterwards the temperature of 180 ℃, melt phase polycondensation 5h under the vacuum tightness of 70Pa.Reaction solution is cooling, then repeatedly dissolve with trichloromethane, washing away not and the covalently bound poly(lactic acid) of Graphene, last at the temperature of 50 ℃ vacuum-drying 24h, obtain GO-g-PLA.
Embodiment 2:
Method by embodiment 1 prepares graphene oxide.
Add afterwards 120ml lactic acid in the 250ml reaction flask, then be placed in the oil bath pan of 100 ℃, underpressure distillation dehydration 4h, obtain anhydrous lactic acid under the vacuum tightness of 300Pa.
Then add the Powdered graphene oxide of 0.5g and 0.3g as the tin protochloride of catalyzer in above-mentioned reaction flask, supersound process 5min, afterwards the temperature of 170 ℃, melt phase polycondensation 8h under the vacuum tightness of 70Pa.Reaction solution is cooling, then repeatedly dissolve with trichloromethane, washing away not and the covalently bound poly(lactic acid) of Graphene, last at the temperature of 50 ℃ vacuum-drying 24h, obtain GO-g-PLA.
Embodiment 3:
Method by embodiment 1 prepares graphene oxide.
Add afterwards 120ml lactic acid in the 250ml reaction flask, then be placed in the oil bath pan of 100 ℃, underpressure distillation dehydration 4h, obtain anhydrous lactic acid under the vacuum tightness of 300Pa.
Then add the Powdered graphene oxide of 0.8g and 0.3g as the stannous octoate of catalyzer in above-mentioned reaction flask, supersound process 5min, afterwards the temperature of 170 ℃, melt phase polycondensation 12h under the vacuum tightness of 70Pa.Reaction solution is cooling, repeatedly dissolve with trichloromethane, washing away not and the covalently bound poly(lactic acid) of Graphene, last at the temperature of 50 ℃ vacuum-drying 24h, obtain GO-g-PLA.
The inventor is to the GO-g-PLA that prepared by above-described embodiment temperature at 30 ℃~700 ℃; carried out the thermogravimetric analysis test under nitrogen protection; thermogravimetric analysis (TG) figure as shown in Figure 1; wherein the right side from down under three curves tackle respectively the GO-g-PLA for preparing in embodiment 3, embodiment 1 and embodiment 2; as can be seen from the figure; the GO-g-PLA that embodiment 1 prepares will decompose 320 ℃ of left and right poly(lactic acid), therefore the percentage of grafting of GO-g-PLA is 25% left and right.The GO-g-PLA that embodiment 2 prepares will decompose 320 ℃ of left and right poly(lactic acid), therefore the percentage of grafting of GO-g-PLA is 30% left and right.The GO-g-PLA that embodiment 3 prepares will decompose 320 ℃ of left and right poly(lactic acid), therefore the percentage of grafting of GO-g-PLA is 20% left and right.

Claims (4)

1. the preparation method of a poly(lactic acid) functionalization graphene, it is characterized in that: described preparation method comprises the following step that carries out in order:
1) adopt improved Hummers method that graphite is prepared into graphite oxide, be dissolved in deionized water after then graphite oxide being washed drying, sonic oscillation and graphite oxide is peeled off, obtain Powdered graphene oxide finally by drying afterwards;
2) lactic acid is placed in reaction vessels, then is placed in the oil bath pan underpressure distillation, obtain anhydrous lactic acid;
3) above-mentioned anhydrous lactic acid is mixed with the mass ratio of graphene oxide with 20: 1~320: 1, be warming up to 160 ℃~190 ℃, add catalyzer, melt phase polycondensation under the vacuum tightness of≤100Pa, carry out cooling after reaction finishes, repeatedly dissolve with trichloromethane afterwards, to wash away not and the covalently bound poly(lactic acid) of Graphene, finally obtain described poly(lactic acid) functionalization graphene (GO-g-PLA).
2. the preparation method of poly(lactic acid) functionalization graphene according to claim 1, it is characterized in that: described step 1), the concentration of ordinary dissolution of graphite oxide in deionized water is 1mg/ml~3mg/ml, the power of sonic oscillation is 100w~1000w, the sonic oscillation time is 2h~5h, and drying temperature is-60 ℃~80 ℃.
3. the preparation method of poly(lactic acid) functionalization graphene according to claim 1 is characterized in that: described step 2), the temperature of oil bath is 90 ℃~120 ℃, and the underpressure distillation time is 2h~5h.
4. the preparation method of poly(lactic acid) functionalization graphene according to claim 1, it is characterized in that: described step 3), catalyzer is stannous octoate or tin protochloride, the mass ratio of anhydrous lactic acid and catalyzer is 1000: 1~50: 1, and the melt phase polycondensation time is 5h~24h.
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Cited By (14)

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Publication number Priority date Publication date Assignee Title
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 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
CN113416313A (en) * 2021-05-25 2021-09-21 暨南大学 Biodegradable compatilizer and preparation method and application thereof
CN114408911A (en) * 2022-01-17 2022-04-29 哈尔滨工业大学 Preparation method of graphene-based aerogel with ultra-fast light-thermal response
CN114437318A (en) * 2022-03-09 2022-05-06 深圳石墨烯创新中心有限公司 Preparation method of graphene oxide-polylactic acid composite material

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JIN TAE YOON ET AL.: "Influences of poly(lactic acid)-grafted carbon nanotube on thermal, mechanical, and electrical properties of poly(lactic acid)", 《POLYMERS ADVANCED TECHNOLOGIES》 *
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
WO2017167135A1 (en) * 2016-03-30 2017-10-05 成都新柯力化工科技有限公司 Graphene microsheet master batch for enhancing bioplastic and preparation method thereof
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
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
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
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 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
CN113416313A (en) * 2021-05-25 2021-09-21 暨南大学 Biodegradable compatilizer and preparation method and application 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
CN114408911A (en) * 2022-01-17 2022-04-29 哈尔滨工业大学 Preparation method of graphene-based aerogel with ultra-fast light-thermal response
CN114437318A (en) * 2022-03-09 2022-05-06 深圳石墨烯创新中心有限公司 Preparation method of graphene oxide-polylactic acid composite material

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Application publication date: 20130508