CN103044664A - 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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- CN103044664A CN103044664A CN201210576005XA CN201210576005A CN103044664A CN 103044664 A CN103044664 A CN 103044664A CN 201210576005X A CN201210576005X A CN 201210576005XA CN 201210576005 A CN201210576005 A CN 201210576005A CN 103044664 A CN103044664 A CN 103044664A
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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 the high molecule nano composite material preparation field, be specially the method that a kind of two-step approach of utilizing the rac-Lactide ring-opening polymerization prepares the polylactic acid/nano diamond composite.
Background technology
Poly(lactic acid) (PLA) be a kind of take lactic acid as raw material the biodegradable Green Polymer Material through chemosynthesis, poly(lactic acid) is nontoxic, nonirritant, have the advantages such as good biocompatibility, easy machine-shaping, therefore, poly(lactic acid) is widely used in biomedicine, industrial or agricultural and daily life field.There are a lot of oxygen-containing functional groups on the surface of Nano diamond, mainly be carbonyl, hydroxyl, carboxyl, ester group, ether and functional group that some are nitrogenous, 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 purpose, obtain the Polymer/nano diamond composite of excellent performance.
The employing nanometer hydroxyapatites (n-HA) such as Jiang Shaopeng and modified grammite are strongthener, method by melt blending has prepared PLA/n-HA/ modified grammite composite material (Jiang Shaopeng, Zhen Weijun, Pang Guilin, Liu Yuee, the Song Xiao beautiful jade tinkling of pieces of jade, yellow east, 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 (to contain-CH
3The DNS of functional group and containing-NH
2The RNS of functional group) nanometer SiO
2It is composite modified to adopt ultrasonic method auxiliary, melt blending that PLLA (PLLA) is carried out, and different nanoparticles is carried out composite modified to poly(lactic acid) (PLLA), has prepared PLLA/ nanometer SiO
2Matrix material (Zhang Puyu, Peng Lichao, Zhang Yudong etc. polylactic acid/nano SiO
2: the thermal characteristics of blend [J]. the polymer circular, 2010,2:107-111.).Ogata etc. adopt N, N-dimethyl two-N-1-18 carbon ammonia chlorides carry out polynite organically-modified, then the blend in chloroform solvent with organo montmorillonite and PLLA, prepared Nano-composite material of poly lactic acid/montmorillonite by solution blended process, and its structure and performance be studied (Ogata N, 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 made poly(lactic acid)/multi-wall carbon nano-tube composite material by solution blending and melt-blending process, improved 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 with the poly(lactic acid) macromolecule dissolution, then with after poly(lactic acid) macromolecular solution and Nano diamond mechanical blending and the drying, obtain the polylactic acid nano diamond composite, and modulus and hardness (the Zhang Q of poly(lactic acid) have been improved, 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 reported the thermostability of material.
It is the small molecules rac-Lactide that the present invention utilizes the intermediate that forms poly(lactic acid), react formation polylactic acid nano diamond composite under certain condition with the Nano diamond of modification, overcome on the one hand the high viscosity disadvantageous effect that dispersion brings to Nano diamond of macromolecular solution, on the other hand, in rac-Lactide ring-opening polymerization process, the rac-Lactide of open loop also can with the Interaction of substituents such as carboxyl on Nano diamond surface, form poly(lactic acid) and the chemical molecular chain that is connected of Nano diamond.
The present invention at first utilizes lactic acid monomer to prepare rac-Lactide, then the rac-Lactide ring-opening polymerization is prepared the polylactic acid/nano diamond composite, and the method has not yet to see any patent and paper report.
Summary of the invention
The objective of the invention is the shortcomings such as relatively poor for pure polylactic resin thermotolerance, that intensity is low, at first utilize lactic acid monomer to prepare rac-Lactide, then rac-Lactide is got the polylactic acid/nano diamond composite by the ring-opening polymerization legal system.
Technical scheme of the present invention is:
A kind of rac-Lactide ring-opening polymerization prepares the method for polylactic acid/nano diamond composite, may further comprise the steps:
Lactic acid and catalyst A are joined in the reactor, be heated to 120 ~ 140 ℃ of lower normal pressure dehydrations, then underpressure distillation during to anhydrous steaming, stops underpressure distillation; Then add glycerine, carry out air distillation at 200 ℃, when extremely steaming without overhead product, stopped reaction; Collect overhead product, suction filtration grinds filter cake to without caking, obtains crude lactide; Then crude lactide is dissolved in the organic solvent, places 80 ℃ of water-baths, treat that it dissolves fully, recrystallization in ice bath, decompress filter is isolated the rac-Lactide crystal, places vacuum drier dry, obtains rac-Lactide; Wherein, material proportion is volume ratio lactic acid: catalyzer: glycerine=50:3:7.
With rac-Lactide obtained above, and catalyzer, Nano diamond and high boiling solvent join in the reactor, and the heating underpressure distillation during to solvent-free steaming, is carried out air distillation, continues to be warming up to 120 ~ 200 ℃, reacting by heating 12 ~ 36h; After reaction is finished, obtain thick product, with ethyl acetate this product is dissolved, and place watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material; Wherein, the 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 the Nano diamond after intermediate product rac-Lactide and the modification to react preparation polylactic acid/nano diamond composite in solution under catalytic condition.Prepared matrix material is a kind of novel material, has improved the thermotolerance of poly(lactic acid).Pure poly(lactic acid) temperature of initial decomposition is 140 ℃, and the temperature of initial decomposition of polylactic acid/nano diamond composite is 240 ℃, has improved about 100 ℃.Wherein the thermal destruction of poly(lactic acid) is mainly caused by the fracture of its ester bond, and ester linkage breaking may be because the free radical reaction that has occured to be caused by terminal hydroxyl and carboxyl, and there is preferably sticking power between the Nano diamond after the modification and poly(lactic acid) matrix, therefore the thermal degradation process that has postponed poly(lactic acid) has improved the resistance toheat of poly(lactic acid).
Description of drawings
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 ℃/min; Atmosphere: N
2)
Embodiment:
Embodiment 1
Measure 50ml lactic acid and the 3ml stannous octoate joins in the single necked round bottom flask, be heated to 120 ℃ of lower normal pressures dehydrations, when white floss occurring, carry out underpressure distillation (vacuum tightness for-0.1MPa), during to anhydrous steaming, stop underpressure distillation; Then add the glycerine of 7ml, receiving bottle is placed ice-water bath, be warming up to 200 ℃ and carry out air distillation, when extremely steaming without overhead product, stopped reaction.With the overhead product in distilled water flushing prolong and the receiving bottle, with the overhead product suction filtration, grind filter cake to without caking, obtain crude lactide.Then crude lactide is dissolved in the dehydrated alcohol of 100ml, places 80 ℃ of water-baths, treat that it dissolves fully, recrystallization in ice bath, decompress filter is isolated 16.45g rac-Lactide crystal, drying for standby.
The dry rac-Lactide of weighing 10g, 0.3g stannous octoate, 0.1g Nano diamond (common commercially available, particle diameter is 10 ~ 80nm), with l00g toluene, join in the single necked round bottom flask, be heated to 150 ℃ carry out underpressure distillation (vacuum tightness for-0.1MPa), when the solvent-free extraction, carry out air distillation, continue to be warming up to 180 ℃, reacting by heating 12h.After reaction is finished, obtain thick product.With this product of 200ml acetic acid ethyl dissolution, place watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material 7.34g.
Show (seeing accompanying drawing 1) through the thermogravimetic analysis (TGA) experiment, decomposing in the time of 260 ℃ of pure poly(lactic acid) is the fastest, and that poly(lactic acid)/diamond nano matrix material decomposes in the time of 270 ℃ is the fastest, pure poly(lactic acid) temperature of initial decomposition is 140 ℃, and the temperature of initial decomposition of poly(lactic acid)/diamond nano matrix material is 240 ℃.By above analysis as can be known, behind the adding Nano diamond, the thermostability of poly(lactic acid) obviously improves, and illustrates that Nano diamond can improve the thermotolerance of poly(lactic acid).
Embodiment 2
Measure 50ml lactic acid and the 3ml stannous octoate joins in the single necked round bottom flask, be heated to 130 ℃ of lower normal pressures dehydrations, when white floss occurring, underpressure distillation (vacuum tightness be-0.1MPa), extremely during anhydrous steaming, stop underpressure distillation; Then add the glycerine of 7ml, receiving bottle is placed ice-water bath, be warming up to 200 ℃ and carry out air distillation, when extremely steaming without overhead product, stopped reaction.With the overhead product in distilled water flushing prolong and the receiving bottle, suction filtration, grind filter cake to without caking, obtain crude lactide.Then crude lactide is dissolved in the dehydrated alcohol of 100ml, places 80 ℃ of water-baths, treat that it dissolves fully, recrystallization in ice bath, decompress filter is isolated the rac-Lactide crystal, drying for standby.
The dry rac-Lactide of weighing 10g, 0.3g stannous octoate, 0.5g Nano diamond (common commercially available, particle diameter is 10 ~ 80nm), with 150g toluene, join in the single necked round bottom flask, be heated to 150 ℃ carry out underpressure distillation (vacuum tightness for-0.1MPa), when the solvent-free extraction, carry out air distillation, continue to be warming up to 180 ℃, reacting by heating 24h.After reaction is finished, obtain thick product.With this product of 200ml acetic acid ethyl dissolution, place watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material 7.73g.
The thermogravimetic analysis (TGA) experimental result is close with embodiment 1.
Embodiment 3
Measure 50ml lactic acid and the 3ml stannous octoate joins in the single necked round bottom flask, be heated to 140 ℃ of lower normal pressures dehydrations, when white floss occurring, underpressure distillation (vacuum tightness be-0.1MPa), extremely during anhydrous steaming, stop underpressure distillation; Then add the glycerine of 7ml, receiving bottle is placed ice-water bath, be warming up to 200 ℃ and carry out air distillation, when extremely steaming without overhead product, stopped reaction.With the overhead product in distilled water flushing prolong and the receiving bottle, suction filtration, grind filter cake to without caking, obtain crude lactide.Then crude lactide is dissolved in the dehydrated alcohol of 100ml, places 80 ℃ of water-baths, treat that it dissolves fully, recrystallization in ice bath, decompress filter is isolated the rac-Lactide crystal, drying for standby.
The dry rac-Lactide of weighing 10g, 0.3g stannous octoate, 0.8g Nano diamond (common commercially available, particle diameter is 10 ~ 80nm), with 200g toluene, join in the single necked round bottom flask, be heated to 150 ℃ carry out underpressure distillation (vacuum tightness for-0.1MPa), when the solvent-free extraction, carry out air distillation, continue to be warming up to 180 ℃, reacting by heating 36h.After reaction is finished, obtain thick product.With this product of 200ml acetic acid ethyl dissolution, place watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material 8.06g.
The thermogravimetic analysis (TGA) experimental result is close with embodiment 1.
Claims (4)
1. a rac-Lactide ring-opening polymerization prepares the method for polylactic acid/nano diamond composite, it is characterized by may further comprise the steps:
Lactic acid and catalyzer are joined in the reactor, be heated to 120 ~ 140 ℃ of lower normal pressure dehydrations, then underpressure distillation during to anhydrous steaming, stops underpressure distillation; Then add glycerine, carry out air distillation at 200 ℃, when extremely steaming without overhead product, stopped reaction; Collect overhead product, suction filtration grinds filter cake to without caking, obtains crude lactide; Then crude lactide is dissolved in the organic solvent, places 80 ℃ of water-baths, treat that it dissolves fully, recrystallization in ice bath, decompress filter is isolated the rac-Lactide crystal, places vacuum drier dry, obtains rac-Lactide; Wherein, material proportion is volume ratio lactic acid: catalyzer: glycerine=50:3:7.
With rac-Lactide obtained above, and catalyzer, Nano diamond and high boiling solvent join in the reactor, and the heating underpressure distillation during to solvent-free steaming, continues to be warming up to 120 ~ 200 ℃, reacting by heating 12 ~ 36h; After reaction is finished, obtain thick product, with this product of acetic acid ethyl dissolution, and place watch-glass dry, obtain poly(lactic acid)/diamond nano matrix material; Wherein, the quality of material proportioning is rac-Lactide: catalyzer: Nano diamond: high boiling solvent=100:3:1 ~ 10:100 ~ 200.
2. rac-Lactide ring-opening polymerization as claimed in claim 1 prepares the method for polylactic acid/nano diamond composite, and it is characterized by described catalyzer is stannous octoate.
3. rac-Lactide ring-opening polymerization as claimed in claim 1 prepares the method for polylactic acid/nano diamond composite, and it is characterized by described organic solvent is dehydrated alcohol, ethyl acetate or benzene-ethyl acetate mixed solvent.
4. rac-Lactide ring-opening polymerization as claimed in claim 1 prepares the method for polylactic acid/nano diamond composite, and it is characterized by described high boiling solvent is toluene, phenyl ether, o-Xylol or methyl-phenoxide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294644A (en) * | 2015-10-09 | 2016-02-03 | 中国科学院长春应用化学研究所 | Preparation method of polymer-grade lactide |
| CN105504236A (en) * | 2016-01-11 | 2016-04-20 | 河南省龙都生物科技有限公司 | Production process for polylactic acid bamboo charcoal slices |
| CN105733000A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Preparation method of polylactic acid film |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309862A (en) * | 1994-05-17 | 1995-11-28 | Toyobo Co Ltd | Production of lactide |
| CN102260405A (en) * | 2011-05-17 | 2011-11-30 | 淮阴工学院 | Preparation method of polylactic acid/attapulgite clay composite material |
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2012
- 2012-12-26 CN CN201210576005.XA patent/CN103044664B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309862A (en) * | 1994-05-17 | 1995-11-28 | Toyobo Co Ltd | Production of lactide |
| CN102260405A (en) * | 2011-05-17 | 2011-11-30 | 淮阴工学院 | Preparation method of polylactic acid/attapulgite clay composite material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733000A (en) * | 2014-12-10 | 2016-07-06 | 黑龙江鑫达企业集团有限公司 | Preparation method of polylactic acid film |
| CN105294644A (en) * | 2015-10-09 | 2016-02-03 | 中国科学院长春应用化学研究所 | Preparation method of polymer-grade lactide |
| 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 |
| CN105504236A (en) * | 2016-01-11 | 2016-04-20 | 河南省龙都生物科技有限公司 | Production process for polylactic acid bamboo charcoal slices |
| 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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