CN106009559A - Preparation method of high-strength and high-toughness PLA (polylactic acid) and in-situ nanofiber composite - Google Patents
Preparation method of high-strength and high-toughness PLA (polylactic acid) and in-situ nanofiber composite Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The invention discloses a preparation method of a high-strength and high-toughness PLA (polylactic acid) and in-situ nanofiber composite. The preparation method is characterized by comprising steps as follows: (1) drying of raw materials: PLA and PBS (poly butylenes succinate) are dried in a drying box, so that the content of water by weight is smaller than 0.01%; (2) melting, blending and extruding: dried PLA and PBS are mixed, sufficiently mixed PLA and PBS are melted and extruded in a double-screw extruder at a high feeding speed and screw speed, treated at a high traction speed and rapidly cooled and cured, and finally, extruded strips are cooled in cold air and then cut into granules; (3) injection molding: firstly, PLA/PBS mixture granules are dried in a constant-temperature blast drying box, the content of water by weight is smaller than 0.01%, then, the dried granules form continuous nanofibers through injection molding equipment capable of applying a high-pressure shearing flow field, and the fully-biodegrade in-situ nanofiber composite with high impact strength, tensile strength and toughness is prepared.
Description
Technical field
The present invention relates to bio-based Process Technology of Polymer technical field, particularly to the preparation method of the polylactic acid in-situ nano fiber composite material of a kind of high impact, hot strength and high tenacity.
Background technology
The development environmentally friendly degradable macromolecule with biomass as raw material can not only gradually be broken away from conventional polymer industry and the dependence of petroleum resources is also helped the impact reduced environment; complying with the sustainable development idea that the whole world is advocated, Ye Shi China breaks through energy bottlenecks as developing country, alleviates the important sticking point of environmental crisis.Recently the full Biodegradable in-situ micro-nano fibrillation risen strengthens blend (M Evstatiev, S Simeonova, K Friedrich, P Formanek.J Mater Sci.2014, DOI:10.1007/s10853-013-7431-5；nullL Xie,H Xu,Z-M Li,B-S Hsiao.Benjamin.Biomacromolecules,2014,15:4054-4064.)，Can in natural environment complete biodegradable and do not discharge any noxious substance (Ojijo Vincent,S-R Suprakas,S Rotimi.ACS Appl.Mater.Interfaces 2012,4,6690-6701.Structural Hierarchy and Polymorphic Transformation in Shear-Induced Shish-Kebab of Stereocomplex Poly(lactic acid).Macromolecular Rapid Communications,2016,37,745-751.)，And performance often can be with advantage (the L Xie such as general engineering plastic compares favourably,H Xu,Z-M Li,B-S Hsiao.Benjamin.Biomacromolecules,2014,15:4054-4064.L Xie,Huan Xu,Benjamin S.Hsiao,GanJi Zhong,ZhongMing Li.ACS Applied Materials&Interfaces,2015,7:8023-8032.)，And cause extensive concern.
In several conventional Biodegradable high-moleculars, polylactic acid (hereinafter referred to as PLA) is because having good degradability, workability and high strength, and raw material sources is extensively (such as sugar or starch), one of the Biodegradable high-molecular becoming research the most extensively and most application prospect (R-E Drumright.Adv Mater, 2000,23:1841-1846.).But, impact strength is poor, fragility is big and poor toughness limits PLA and is more widely applied.Therefore obtain complete biodegradable toughening type PLA goods and there is huge challenge, especially realize technical grade and produce.Applicant's current research finds to use substep coupling mechanism (i.e. to apply the field of flow of different qualities at different processing stages, control blend phase morphology and realize Morphological Transitions), biodegradable poly butylene succinate (hereinafter referred to as PBS) good for toughness is added in PLA matrix, utilize the shear flow field that in extrusion Blending Processes, (double screw extruder) produces to prepare nanoscale PBS dispersion phase, and be uniformly distributed in PLA matrix；Further, the elongational flow field that (single screw rod sheet extruder) is formed during extrusion molding successfully realizes the transformation to PBS nanofiber of the PBS nano-particle, finally realize PLA in-situ composite thin film hot strength, Young's modulus and elongation at break and increase substantially (L Xie simultaneously, H Xu, Z-M Li, B-S Hsiao.Benjamin.Biomacromolecules, 2014,15:4054-4064.).
Processing molding method as PLA/PBS fully bio-degradable nano composite material, we use the research means of substep coupling, at blended stage (double screw extruder), shear flow field is utilized to control PBS dispersed phase size, realize the preorientation of PBS nanodispersed phase and pre-deformation simultaneously, wherein, in extrusion, pre-deformation and the preorientation of dispersion phase are not reported in the research work of early stage；In formative stage (injection mo(u)lding), utilize the high shear field of flow formed in injection molding process, it is achieved the transformation of preorientation PBS dispersion phase to continuous nano-fibre, not use the method that fiber is induced in tradition elongational flow field.Finally in the enhancement effect of nanofiber, and under the strong interface that brings of nano effect interacts, it is achieved PLA/PBS receives high impact strength, hot strength and the elongation at break of fiber composite material in situ.If the expansion of this co-mixing system can be beneficial to us to injection molding process to explore the morphology control method of more universality, it is advantageously implemented the industrialized production of high-performance PLA goods, also the methodology of " field of flow realizes blend and determines structure ", and the technological means of abundant PLA blend morphology regulation and control will be checked.Promote that we effectively utilize natural resources, lead plastic processing industry to go on Sustainable Development Road further.
From the point of view of in terms of patent, the patent of PLA/PBS nano-fiber composite material is prepared in the controllable flow field the most not utilizing distribution design, has no by preparing the Patents that biodegradable in-situ nano fiber obtains the PLA goods of high impact resistance, high intensity and high elongation at tear.The patent realizing PLA performance optimization at present mainly includes that fibrous material strengthens PLA and high-ductility polymer toughening PLA.Such as: method (Chinese invention patent, the publication number CN101168617 of PLA toughening modifying；Publication number CN1760266)；A kind of preparation method (Chinese invention patent, publication number CN101570624) of bio-based PLA composite；A kind of preparation method (Chinese invention patent, publication number CN101948613A CN104357953A) of toughening type PLA composite fibre.
Summary of the invention
The technical problem to be solved in the present invention is: offer is prepared in-situ nano fiber and realized PLA goods high impact resistance, high intensity and the new method of high elongation at tear, be there is the field of flow of different qualities by Multiple-step mode, that is, stretching/shear flow field (twin-screw extrusion is blended) is utilized to realize nanorize and the preorientation of dispersion phase.Use injection mo(u)lding processing method, realize PBS fibrosis in PLA matrix, realize nanodispersed phase fibrosis in PLA matrix of preorientation, thus promoting half crystal formation PLA crystallization, the common effect eventually through the PBS with moderate degree of crystallinity, the PLA of the degree of orientation and high length-diameter ratio realizes the regulation and control to PLA impact strength, mechanical strength and elongation at break.
The technical scheme is that the polylactic acid of a kind of high-intensity high-tenacity receives in situ the preparation method of fiber composite material, comprise the steps of (1) raw material drying: polylactic acid and poly butylene succinate are dried in an oven, make moisture weight content less than 0.01%；(2) melt blending extrusion: gained is dried polylactic acid and poly butylene succinate by mixing, well-mixed PLA/PBS uses high rate of feeding and screw speed to melt extrude in double screw extruder, use high pulling speed and quickly cooling and solidifying, pelletizing after finally the material strip of extrusion being cooled down in cold air simultaneously；(3) injection mo(u)lding: first polylactic acid/poly butylene succinate mixture pellet is dried in constant temperature convection oven, make moisture weight content less than 0.01%, then dried pellet is used the injection molding apparatus applying high shear field of flow, forming continuous nano-fibre, the original position of the complete biodegradable preparing high impact, hot strength and high tenacity receives fiber composite material.
The mass ratio of PLA/PBS is: 9:1-3:2.
Described polylactic acid be relative molecular mass at 5～400,000 grams/mol, the relative molecular mass of described poly butylene succinate is 6-30 ten thousand grams/mol.
In described step (2), the barrel first paragraph of described double screw extruder to the 7th section and die temperature are respectively set as 80,120,150,160,170,170 and 165 DEG C.
In described step (2), screw speed 200-350 turns/min, and rate of feeding is 100-250g/min, and traction rate of extension is that 200-350 turns/min, and the temperature of cold air wind is less than 20 DEG C.
In described step (3), described high pressure is 60～80MPa, and the dwell time is 30-50s.
In described step (3), the barrel first paragraph of described injection machine to the 5th section and die temperature are respectively set as 130,160,165,170 and 165 DEG C, and the temperature of cold air wind is less than 20 DEG C.
Beneficial effects of the present invention:
High rate of feeding and screw speed is used to obtain the polylactic acid containing nanoparticle and polybutylene succinate polyblend in the technique of the present invention, stage is blended at twin-screw extrusion, well-mixed polylactic acid/poly butylene succinate, double screw extruder melt extrudes, mainly by improving screw speed increase melt and screw rod, the Strong shear field that friction between melt and cartridge wall is formed, most importantly high pulling speed is used to form elongational flow field, dispersion phase molten drop is forced to occur broken and preorientation and pre-deformation occur, use simultaneously high feed speed and quickly cooling and solidifying reduce and crushed probability that molten drop reassociates and kept preorientation structure.
The present invention receives in situ the combination property of fiber composite material by investigating, and specifically includes shock resistance and hot strength, modulus and elongation at break.And by scanning electron microscope and SAXS and WAXD X-ray, provide the information of fiber composite material external morphology and configuration aspects received in situ, including size, the degree of crystallinity of nanofiber, and degree of orientation.The original position of PLA/PBS complete biodegradable prepared by the method is received fiber composite material and is had the morphosis feature that nanofiber major diameter is more moderate than the high and basic degree of crystallinity of PLA and the degree of orientation.And measure according to the method provided in ASTM D-638, rate of extension is 20mm/min, experimental temperature is 23 DEG C, increase (0～100%) with fiber content, impact strength (5.6KJ/m2) relative to pure PLA, PLA/PBS receives in situ fiber composite material and is respectively increased 1256%, 3039%, 1822% and 7133%；And elongation at break is 13.4,31.6,23 and 75 times of pure PLA (5%) respectively.Although it addition, the mechanical strength that the hot strength of PBS only has 35MPa, PLA/PBS composite still can reach 69MPa.Therefore, by regulating the content of fiber, can obtain and there is the original position of high impact, hot strength, modulus and elongation at break receive fiber composite material.
It addition, present invention additionally comprises following beneficial effect:
1) this patent uses the technique of first melt blending common molding (extrude, be molded) again to obtain biodegradable composites, and usual injection machine is used equally to build this production line, implements easily；
2) PBS is a kind of the most biodegradable macromolecular material of degradation rate, it is thus achieved that PLA/PBS receive in fiber composite material in situ, its biodegradable characteristics can't be damaged, the degradation rate of whole system can be improved on the contrary；
3) by the regulation and control impact strength of PLA, hot strength and toughness are blended, it is not necessary to material carries out any process or modification, and commercially available material can meet requirement, and therefore, this patent is easily implemented, it is not necessary to high investment；
4) the simple PBS that adds can only have one-side improvement to PLA performance, be usually good toughness and intensity is low, the present invention uses the PBS nanofiber regulation and control PLA performance being formed in situ, obtain the original position of high impact, hot strength and toughness and receive fiber composite material, be conducive to expanding the application market of PLA.
Accompanying drawing explanation
Fig. 1, for be studied by imitative spider silk, prepares the process of PBS nanofiber, from the process of the nanodispersed phase of preorientation to nanofiber；
Fig. 2 is the electron scanning micrograph of PBS nanofiber morphologic observation, and test sample is taken from by PLA Yu the PBS nano-fibre blend thing than row mixing.The cross-section morphology and (3) that do not etch sample after specifically including that the preorientation nano-size dispersion phase structure and (2) injection mo(u)lding that (1) twin screw basis obtains etchs the pattern after PLA completely, and etching operation i.e. etches away PLA body portion at dichloromethane placement 40s；
Fig. 3 is by the PLA mixed than row and/PBS nano-fiber composite material infrared spectrogram；
Fig. 4 is the pattern after partial etching PLA, and etching operation the most first places 24 hours to etch away PLA body portion in the mixed solution of water, methanol and sodium hydroxide；
Fig. 5 is to receive two dimension wide angle scatter diagram (A) of fiber composite material, one-dimensional wide angle scattering strength figure (B), PLA (200)/(110) crystal face azimuth (C), PBS (110) crystal face azimuth (D) and two dimension small-angle scattering figure (E) in situ by PLA and PBS mixed than row；
Fig. 6 is to receive in situ the lamellar structure of fiber composite material and lamellae thickness by than PLA and PBS of row mixing；
Fig. 7 is by receiving in situ the thermal behavior curve chart of fiber composite material than PLA and PBS of row mixing；
Fig. 8 is by the degree of crystallinity of PLA and PBS in the PLA/PBS nanosheet composite material than row mixing；
Fig. 9 is the Mechanics Performance Testing figure by PLA and the PBS nanosheet composite material than row mixing；
Figure 10 is cross-section morphology figure after the Mechanics Performance Testing by PLA and the PBS nanosheet composite material than row mixing.
Detailed description of the invention
Embodiment 1-4
(1) raw material drying: PLA and PBS is dried 12 hours in the convection oven of constant temperature 80 DEG C；
(2) melt blending extrusion: gained is dried PLA and PBS and mixes in different quality ratio.Wherein the content of poly-succinic acid-butanediol is 0%, 10%, 20%, 40%, 60%, 100% respectively.Well-mixed PLA/PBS uses high rate of feeding and screw speed to melt extrude in double screw extruder, it is thus achieved that PLA and the PBS blend containing nanoparticle.Finally the material strip of extrusion is exposed to sufficiently cool rear pelletizing in cold air.Its concrete formula is shown in Table 1, and extrusion blending technology parameter is shown in Table 2；
(3) product molding: be first dried 8 hours in the convection oven of constant temperature 80 DEG C by PLA/PBS mixture, makes moisture weight content less than 0.01%, then dried pellet is used injection molding process.Prepare high intensity and the adjustable fully bio-degradable of toughness and receive fibrillation blend, and the degree of orientation of nanofiber and degree of crystallinity have controllability.Finally the fine blend of receiving of this dumbbell shaped is dried 8 hours in the convection oven of 80 DEG C, makes moisture weight content less than 0.01%.Concrete molding technique parameter is shown in Table 3；Melting curve is shown in Table 4；Mechanical property is shown in Table 5.
Table 1
Table 2 twin screw melt extrudes blending technology parameter 130,170,170,170 and 165 DEG C
Fiber composite material preparation technology parameter received in situ by table 3
Performance: in order to investigate the impact on PLA/PBS composite various aspects of performance of the PBS nanofiber, has mainly carried out composite utilizing the test of thermal performance analysis, impact property and extension test analysis.Utilizing differential heating scan instrument (DSC Q200, U.S. TA) to be analyzed hot property, rise to 200 DEG C with the heating rate of 3 DEG C/min from 40, be tested the hot property of goods, test result is shown in Table 4.Utilize tester for elongation (Instron 5576, U.S. TA) and impact test instrument, measure according to the method provided in ASTM D-638, rate of extension is 50mm/min, being tested the tensile property of goods under room temperature (23 DEG C), intensity and the toughness of material increase substantially.Along with PBS content is from 10%, 20%, 40% increases to 60%, the impact strength (5.6MJ/m3) relative to pure PLA, and PLA/PBS receives in situ fiber composite material and is respectively increased 1256%, 3039%, 1822% and 7133%；And elongation at break is 13.4,31.6,23 and 75 times of pure PLA (5%) respectively.Although it addition, the mechanical strength that the hot strength of PBS only has 35MPa, PLA/PBS composite still can reach 69MPa, being shown in Table 5；Visible, the formation of PBS nanofiber can step up intensity and the toughness of PLA.In sum, the formation of PBS ester nanofiber can improve material impact intensity, hot strength and toughness, it is achieved that design and the regulation and control to PLA comprehensive mechanical property, is conducive to expanding the range of application of PLA.
The thermal behavior of table 4 composite
The mechanical property performance of table 5 composite
Tensiled fractography is observed: in order to after observing stretching, PLA/PBS receives in situ the dispersion of Nanowire fiber and the interface conditions with PLA matrix thereof in fiber composite material, by PLA/PBS composite, at mixed solution, (water is 1:2 with the volume ratio of methanol, the concentration of sodium hydroxide is 0.025mol/L) in place 12 hours to etch away body portion, streamwise is (model JEOLSJM-900VL under scanning electron microscope, Japanese strain formula meeting) observe, see accompanying drawing 10；Being not difficult to find out, nanofiber has good dispersion in the base and has good interface interaction with PLA matrix, and these are conducive to transmitting stress in drawing process, it is thus achieved that the PLA/PBS composite of high intensity and high tenacity.
Claims (7)
1. the polylactic acid of high-intensity high-tenacity receives in situ a preparation method for fiber composite material, and it is special
Levy and be: comprise the steps of (1) raw material drying: by polylactic acid and poly-succinic fourth
Diol ester is dried in an oven, makes moisture weight content less than 0.01%；(2) melt altogether
Mixed extrusion: gained is dried polylactic acid and poly butylene succinate by mixing, the most mixed
The PLA/PBS closed uses high rate of feeding and screw speed molten in double screw extruder
Melt extrusion, use high pulling speed simultaneously and quickly cool and solidify, the material finally will extruded
Bar cool down in cold air after pelletizing；(3) injection mo(u)lding: first by polylactic acid/poly-succinic
Butanediol ester mixture pellet is dried in constant temperature convection oven, makes moisture weight content few
In 0.01%, then dried pellet is used the injection applying high shear field of flow
Former, forms continuous nano-fibre, prepares high impact, hot strength and height
The original position of the complete biodegradable of toughness receives fiber composite material.
The polylactic acid of a kind of high-intensity high-tenacity the most according to claim 1 is received fine compound in situ
The preparation method of material, it is characterised in that: the mass ratio of PLA/PBS is: 9:1-3:2.
The polylactic acid of a kind of high-intensity high-tenacity the most according to claim 1 and 2 receives fibre in situ
The preparation method of composite, it is characterised in that: described polylactic acid is average molecular matter
Measure at 5～400,000 grams/mol, the relative molecular mass of described poly butylene succinate
6-30 ten thousand grams/mol.
The polylactic acid of a kind of high-intensity high-tenacity the most according to claim 1 is received fine compound in situ
The preparation method of material, it is characterised in that: in step (2), described double screw extruder
Barrel first paragraph to the 7th section and die temperature be respectively set as 80,120,150,160,
170,170 and 165 DEG C.
The polylactic acid of a kind of high-intensity high-tenacity the most according to claim 1 is received fine compound in situ
The preparation method of material, it is characterised in that: in step (2), screw speed 200-350
Turning/min, rate of feeding is 100-250g/min, and traction rate of extension is 200-350
Turning/min, the temperature of cold air wind is less than 20 DEG C.
The polylactic acid of a kind of high-intensity high-tenacity the most according to claim 1 is received fine compound in situ
The preparation method of material, it is characterised in that: in step (3), described high pressure is 60～80MPa,
Dwell time is 30-50s.
The polylactic acid of a kind of high-intensity high-tenacity the most according to claim 1 is received fine compound in situ
The preparation method of material, it is characterised in that: in step (3), the barrel of described injection machine
First paragraph is respectively set as 130,160,165,170 Hes to the 5th section and die temperature
165 DEG C, the temperature of cold air wind is less than 20 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727752A (en) * | 2018-06-11 | 2018-11-02 | 中原工学院 | A method of preparing high strength poly vinyl alcohol composite hydrogel using in-situ fibrillation |
| CN110903620A (en) * | 2019-11-28 | 2020-03-24 | 华南理工大学 | Fully biodegradable serial crystal high-heat-resistance polylactic acid composite material and preparation method thereof |
-
2016
- 2016-05-18 CN CN201610328864.5A patent/CN106009559A/en active Pending
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| LAN XIE,ET AL.: "Unprecedented Access to Strong and Ductile Poly(lactic acid) by Introducing In Situ Nanofibrillar Poly(butylene succinate) for Green Packaging", 《BIOMACROMOLECULES》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727752A (en) * | 2018-06-11 | 2018-11-02 | 中原工学院 | A method of preparing high strength poly vinyl alcohol composite hydrogel using in-situ fibrillation |
| CN108727752B (en) * | 2018-06-11 | 2021-02-05 | 中原工学院 | Method for preparing high-strength polyvinyl alcohol composite hydrogel by utilizing in-situ fiber forming |
| CN110903620A (en) * | 2019-11-28 | 2020-03-24 | 华南理工大学 | Fully biodegradable serial crystal high-heat-resistance polylactic acid composite material and preparation method thereof |
| CN110903620B (en) * | 2019-11-28 | 2021-08-10 | 华南理工大学 | Fully biodegradable serial crystal high-heat-resistance polylactic acid composite material and preparation method thereof |
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