CN103044664B - Method for preparing polylactide/nanodiamond composite material through lactide ring opening polymerization - Google Patents
Method for preparing polylactide/nanodiamond composite material through lactide ring opening polymerization Download PDFInfo
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- CN103044664B CN103044664B CN201210576005.XA CN201210576005A CN103044664B CN 103044664 B CN103044664 B CN 103044664B CN 201210576005 A CN201210576005 A CN 201210576005A CN 103044664 B CN103044664 B CN 103044664B
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Abstract
The invention discloses a method for preparing a polylactide/nanodiamond composite material through lactide ring opening polymerization. The method comprises the following steps of: adding lactic acid and a catalyst into a reactor, heating to 120-140 DEG C, performing atmospheric dehydration, performing reduced pressure distillation till no water is distilled out, and stopping the reduced pressure distillation; adding glycerol, performing atmospheric distillation at 200 DEG C till no distillate is distilled out, and stopping reaction; purifying the distillate to obtain lactide; adding the obtained lactide, and the catalyst, nanodiamond and a high-boiling point solvent into the reactor, heating, performing reduced pressure distillation till no solvent is distilled out, performing atmospheric distillation, further heating to 120-200 DEG C, and heating and reacting for 12-36 hours; and purifying and drying a reaction product to obtain the polylactide/nanodiamond composite material. In the method, the initial decomposing temperature of the polylactide/nanodiamond composite material is increased by about 100 DEG C.
Description
Technical field
The invention belongs to high molecule nano composite material preparation field, be specially a kind of method utilizing the two-step approach of rac-Lactide ring-opening polymerization to prepare polylactic acid/nano diamond composite.
Background technology
Poly(lactic acid) (PLA) is a kind of take lactic acid as the biodegradable Green Polymer Material of raw material through chemosynthesis, poly(lactic acid) is nontoxic, nonirritant, there is the advantages such as excellent biocompatibility, easily machine-shaping, therefore, poly(lactic acid) is widely used in biomedicine, industrial or agricultural and daily life field.There is a lot of oxygen-containing functional group on the surface of Nano diamond, mainly carbonyl, hydroxyl, carboxyl, ester group, ether and some nitrogenous functional groups, and these surface groups are had an effect with polymkeric substance possibly by modification, this effect can make Nano diamond and polymeric matrix good combination, reach polymer-modified object, obtain the Polymer/nano diamond composite of excellent performance.
Jiang Shaopeng etc. adopt nanometer hydroxyapatite (n-HA) and modified grammite to be strongthener, PLA/n-HA/ modified grammite composite material (Jiang Shaopeng has been prepared by the method for melt blending, Zhen Weijun, Pang Guilin, Liu Yuee, the Song Xiao beautiful jade tinkling of pieces of jade, Huang Dong, He Shengxi. the preparation of polylactic acid/nano-hydroxyapatite/modified grammite composite material, sign and performance study, nonmetalliferous ore (periodical), 2010,33(3): 16-19).Zhang Puyu etc. utilize two kinds of different functional groups (containing-CH
3the DNS of functional group and containing-NH
2the RNS of functional group) Nano-meter SiO_2
2the method of employing ultrasonic wave added, melt blending is carried out composite modified to PLLA (PLLA), carries out composite modified, prepared PLLA/ Nano-meter SiO_2 by different nanoparticles to poly(lactic acid) (PLLA)
2matrix material (Zhang Puyu, Peng Lichao, Zhang Yudong etc. polylactic acid/nano SiO
2: the thermal characteristics [J] of blend. polymer is circulated a notice of, 2010,2:107-111.).Ogata etc. adopt N, polynite is carried out organically-modified by N-dimethyl two-N-1-18 carbon ammonia chloride, then by organo montmorillonite and PLLA blended in chloroform solvent, Nano-composite material of poly lactic acid/montmorillonite has been prepared by solution blended process, and (Ogata N is studied to its stuctures and properties, Jimenez G, Kawai H, et al.Structure and Thermal/Mechanical Properties of Poly (L-Lactide)-Clay Blend [J] .Joumal of Polymer Science PartB:Polymer Physics.1997, 35 (2): 389-396.).Moon etc. have obtained poly(lactic acid)/multi-wall carbon nano-tube composite material by solution blending and melt-blending process, improve shielding electromagnetic waves effect and thermostability, but tensile strength and elongation at break reduce (Moon S I, Jin F, Lee C, et al.Novel Carbon Nanotube/Poly (L-Lactic Acid) Nanocomposites:Their Modulus, Thermal Stability, and Electrical Conductivity [J] .Macromol Symp2005,224:287-295).Zhang Q etc. are by poly(lactic acid) macromolecule dissolution, then by poly(lactic acid) macromolecular solution and Nano diamond mechanical blending and after drying, obtain polylactic acid nano diamond composite, and improve modulus and hardness (the Zhang Q of poly(lactic acid), Mochalin V, Neitzel I, et al.Fluorescent PLLA-nanodiamond composites for bone tissue engineering [J] .Biomaterials2011, 32:87-94), but the reunion of Nano diamond in poly(lactic acid) is serious, well do not disperseed, and do not report the thermostability of material.
The present invention utilizes the intermediate and small molecules rac-Lactide that form poly(lactic acid), react under certain condition with the Nano diamond of modification and form polylactic acid nano diamond composite, the high viscosity overcoming on the one hand macromolecular solution disperses the disadvantageous effect brought to Nano diamond, on the other hand, in rac-Lactide ring opening polymerisation process, the rac-Lactide of open loop also can with the Interaction of substituents such as the carboxyl on Nano diamond surface, form the poly(lactic acid) molecular chain that be connected chemical with Nano diamond.
First the present invention utilizes lactic acid monomer to prepare rac-Lactide, then polylactic acid/nano diamond composite is prepared in rac-Lactide ring-opening polymerization, and the method has not yet to see any patent and paper report.
Summary of the invention
The object of the invention is the shortcomings such as poor for pure polylactic resin thermotolerance, intensity is low, first utilize lactic acid monomer to prepare rac-Lactide, then rac-Lactide is obtained polylactic acid/nano diamond composite by ring-opening polymerization legal system.
Technical scheme of the present invention is:
A method for polylactic acid/nano diamond composite is prepared in rac-Lactide ring-opening polymerization, comprises the following steps:
Join in reactor by lactic acid and catalyst A, normal pressure dehydration at being heated to 120 ~ 140 DEG C, then underpressure distillation, during to anhydrous steaming, stops underpressure distillation; Then add glycerine, carry out air distillation at 200 DEG C, to when steaming without overhead product, stopped reaction; Collect overhead product, suction filtration, grinding filter cake, to without caking, obtains crude lactide; Then crude lactide is dissolved in organic solvent, is placed in 80 DEG C of water-baths, treats that it dissolves completely, recrystallization in ice bath, decompress filter, isolate rac-Lactide crystal, be placed in vacuum drier dry, obtain rac-Lactide; Wherein, material proportion is volume ratio lactic acid: catalyzer: glycerine=50:3:7.
By rac-Lactide obtained above, and catalyzer, Nano diamond and high boiling solvent join in reactor, heating underpressure distillation, during to solvent-free steaming, carry out air distillation, continue to be warming up to 120 ~ 200 DEG C, reacting by heating 12 ~ 36h; After having reacted, obtain thick product, by ethyl acetate, this product is dissolved, and it is dry to be placed in watch-glass, obtains poly(lactic acid)/diamond nano matrix material; Wherein, quality of material proportioning is rac-Lactide: catalyzer: Nano diamond: high boiling solvent=100:3:1 ~ 10:100 ~ 200.
Described catalyzer is stannous octoate.
Described organic solvent is dehydrated alcohol, ethyl acetate or benzene-ethyl acetate mixed solvent.
Described high boiling solvent is toluene, phenyl ether, o-Xylol or methyl-phenoxide.
Beneficial effect of the present invention is: utilize the mixture of intermediate product rac-Lactide and modified Nano diamond to react under catalytic condition in the solution and prepare polylactic acid/nano diamond composite.Prepared matrix material is a kind of novel material, improves the thermotolerance of poly(lactic acid).Pure poly(lactic acid) temperature of initial decomposition is 140 DEG C, and the temperature of initial decomposition of polylactic acid/nano diamond composite is 240 DEG C, improves about 100 DEG C.Wherein the thermal destruction of poly(lactic acid) causes primarily of the fracture of its ester bond, and ester linkage breaking may be because there occurs the free radical reaction caused by terminal hydroxyl and carboxyl, and between modified Nano diamond and poly(lactic acid) matrix, there is good sticking power, be delayed the thermal degradation process of poly(lactic acid), therefore improve the resistance toheat of poly(lactic acid).
Accompanying drawing explanation
Fig. 1. the hot weightless picture of pure poly(lactic acid) and poly(lactic acid)/diamond nano matrix material, wherein a: pure poly(lactic acid), b: poly(lactic acid) diamond nano matrix material; (temperature rise rate: 10 DEG C/min; Atmosphere: N
2)
Embodiment:
Embodiment 1
Measure 50ml lactic acid and 3ml stannous octoate joins in single necked round bottom flask, at being heated to 120 DEG C, normal pressure dehydration, when there is White Flocculus, carries out underpressure distillation (vacuum tightness be-0.1MPa), during to anhydrous steaming, and stopping underpressure distillation; Then add the glycerine of 7ml, receiving bottle is placed in ice-water bath, be warming up to 200 DEG C and carry out air distillation, to when steaming without overhead product, stopped reaction.With the overhead product in distilled water flushing prolong and receiving bottle, by overhead product suction filtration, grinding filter cake, to without caking, obtains crude lactide.Then crude lactide is dissolved in the dehydrated alcohol of 100ml, is placed in 80 DEG C of water-baths, treats that it dissolves completely, recrystallization in ice bath, decompress filter, isolate 16.45g rac-Lactide crystal, drying for standby.
Weigh the dry rac-Lactide of 10g, the stannous octoate of 0.3g, the Nano diamond (common commercially available, particle diameter is 10 ~ 80nm) of 0.1g, with l00g toluene, join in single necked round bottom flask, be heated to 150 DEG C and carry out underpressure distillation (vacuum tightness is-0.1MPa), during to solvent-free extraction, carry out air distillation, continue to be warming up to 180 DEG C, reacting by heating 12h.After having reacted, obtain thick product.With this product of 200ml acetic acid ethyl dissolution, be placed in watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material 7.34g.
Show (see accompanying drawing 1) through thermogravimetic analysis (TGA) experiment, decomposing 260 DEG C time of pure poly(lactic acid) is the fastest, and poly(lactic acid)/diamond nano matrix material decomposes the fastest 270 DEG C time, pure poly(lactic acid) temperature of initial decomposition is 140 DEG C, and the temperature of initial decomposition of poly(lactic acid)/diamond nano matrix material is 240 DEG C.From analyzing above, after adding Nano diamond, the thermostability of poly(lactic acid) significantly improves, and illustrates that Nano diamond can improve the thermotolerance of poly(lactic acid).
Embodiment 2
Measure 50ml lactic acid and 3ml stannous octoate joins in single necked round bottom flask, normal pressure dehydration at being heated to 130 DEG C, when there is White Flocculus, underpressure distillation (vacuum tightness be-0.1MPa), during to anhydrous steaming, stopping underpressure distillation; Then add the glycerine of 7ml, receiving bottle is placed in ice-water bath, be warming up to 200 DEG C and carry out air distillation, to when steaming without overhead product, stopped reaction.With the overhead product in distilled water flushing prolong and receiving bottle, suction filtration, grinding filter cake, to without caking, obtains crude lactide.Then crude lactide is dissolved in the dehydrated alcohol of 100ml, is placed in 80 DEG C of water-baths, treats that it dissolves completely, recrystallization in ice bath, decompress filter, isolate rac-Lactide crystal, drying for standby.
Weigh the dry rac-Lactide of 10g, the stannous octoate of 0.3g, the Nano diamond (common commercially available, particle diameter is 10 ~ 80nm) of 0.5g, with 150g toluene, join in single necked round bottom flask, be heated to 150 DEG C and carry out underpressure distillation (vacuum tightness is-0.1MPa), during to solvent-free extraction, carry out air distillation, continue to be warming up to 180 DEG C, reacting by heating 24h.After having reacted, obtain thick product.With this product of 200ml acetic acid ethyl dissolution, be placed in watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material 7.73g.
Thermogravimetic analysis (TGA) experimental result is close with embodiment 1.
Embodiment 3
Measure 50ml lactic acid and 3ml stannous octoate joins in single necked round bottom flask, normal pressure dehydration at being heated to 140 DEG C, when there is White Flocculus, underpressure distillation (vacuum tightness be-0.1MPa), during to anhydrous steaming, stopping underpressure distillation; Then add the glycerine of 7ml, receiving bottle is placed in ice-water bath, be warming up to 200 DEG C and carry out air distillation, to when steaming without overhead product, stopped reaction.With the overhead product in distilled water flushing prolong and receiving bottle, suction filtration, grinding filter cake, to without caking, obtains crude lactide.Then crude lactide is dissolved in the dehydrated alcohol of 100ml, is placed in 80 DEG C of water-baths, treats that it dissolves completely, recrystallization in ice bath, decompress filter, isolate rac-Lactide crystal, drying for standby.
Weigh the dry rac-Lactide of 10g, the stannous octoate of 0.3g, the Nano diamond (common commercially available, particle diameter is 10 ~ 80nm) of 0.8g, with 200g toluene, join in single necked round bottom flask, be heated to 150 DEG C and carry out underpressure distillation (vacuum tightness is-0.1MPa), during to solvent-free extraction, carry out air distillation, continue to be warming up to 180 DEG C, reacting by heating 36h.After having reacted, obtain thick product.With this product of 200ml acetic acid ethyl dissolution, be placed in watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material 8.06g.
Thermogravimetic analysis (TGA) experimental result is close with embodiment 1.
Claims (1)
1. a method for polylactic acid/nano diamond composite is prepared in rac-Lactide ring-opening polymerization, it is characterized by and comprises the following steps:
Join in reactor by lactic acid and catalyzer, normal pressure dehydration at being heated to 120 ~ 140 DEG C, then underpressure distillation, during to anhydrous steaming, stops underpressure distillation; Then add glycerine, carry out air distillation at 200 DEG C, to when steaming without overhead product, stopped reaction; Collect overhead product, suction filtration, grinding filter cake, to without caking, obtains crude lactide; Then crude lactide is dissolved in organic solvent, is placed in 80 DEG C of water-baths, treats that it dissolves completely, recrystallization in ice bath, decompress filter, isolate rac-Lactide crystal, be placed in vacuum drier dry, obtain rac-Lactide; Wherein, material proportion is volume ratio lactic acid: catalyzer: glycerine=50:3:7;
By rac-Lactide obtained above, and catalyzer, Nano diamond and high boiling solvent join in reactor, heating underpressure distillation, during to solvent-free steaming, continue to be warming up to 120 ~ 200 DEG C, reacting by heating 12 ~ 36h; After having reacted, obtain thick product, with this product of acetic acid ethyl dissolution, and it is dry to be placed in watch-glass, obtains poly(lactic acid)/diamond nano matrix material; Wherein, quality of material proportioning is rac-Lactide: catalyzer: Nano diamond: high boiling solvent=100:3:1 ~ 10:100 ~ 200;
Described catalyzer is stannous octoate;
Described organic solvent is dehydrated alcohol, ethyl acetate or benzene-ethyl acetate mixed solvent;
Described high boiling solvent is toluene, phenyl ether, o-Xylol or methyl-phenoxide.
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| CN105294644B (en) * | 2015-10-09 | 2018-10-16 | 中国科学院长春应用化学研究所 | A kind of preparation method of polymer grade lactide |
| CN105504236B (en) * | 2016-01-11 | 2018-06-26 | 河南省龙都生物科技有限公司 | Polylactic acid bamboo charcoal is sliced production technology |
| CN106806944A (en) * | 2016-12-27 | 2017-06-09 | 河南省豫星华晶微钻有限公司 | Modified PLA base bone material of a kind of nanometer carbon crystal and preparation method thereof |
| CN111454437A (en) * | 2020-04-24 | 2020-07-28 | 张中明 | High-thermal-conductivity carbon nanotube modified polylactic acid material and preparation method thereof |
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