CN104910422B - One kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose and preparation method thereof - Google Patents
One kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose and preparation method thereof Download PDFInfo
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Abstract
The invention discloses one kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose and preparation method thereof.One kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose, its raw material components include：45 67 parts of 30 50 parts of high length-diameter ratio nano-cellulose, 35 parts of ionomer and PLA, the number are mass fraction, and the draw ratio of high length-diameter ratio nano-cellulose is more than 100.The present invention enhanced lactic acid composite material of high length-diameter ratio nano-cellulose, any chemical reagent is not used, and nontoxic pollution-free is a kind of method for pretreating of environmental protection；Fiber is punctured in PLA matrix with three-dimensional netted filament structure, the fracture mode of gained composite is ductile rupture, the mechanical strength of existing poly-lactic acid material is significantly improved, especially toughness, while also considerably improving the thermal stability of poly-lactic acid material.
Description
Technical field
The present invention relates to one kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose and preparation method thereof, category
In field of compound material.
Background technology
With a large amount of consumption of petroleum resources, the growing day by day of plastic garbage causes troubling environmental crisis, in vain
Color pollution becomes increasingly severe, how to solve this problem and is paid attention to by various countries, wherein an important approach is exactly
Exploitation biodegradable polymer.
In numerous biodegradable polymers, PLA (PLA) biodegradability is good, mechanical strength is moderate, plus
Work performance is good, it is most important that it comes from nature, is attributed to nature, real to realize carbon cycle and turn into the research of current scholar
Focus.But PLA also has many problem and shortage parts, such as heat resistance is poor, toughness is relatively low and engineering plastics
More low compared to mechanical strength, the problem in terms of these physical properties greatly have impact on the practical application of PLA.
CNF (biomass nano cellulose) is a kind of extremely abundant polysaccharide biomaterial of nature reserves, is deposited extensively
In being the green bio material such as timber, bamboo wood, linen-cotton and agricultural crop straw.Because having raw material renewable, inexpensive, low close
The features such as degree, high specific strength, good biocompatibility, degradable, reusable edible, it is widely used in strengthening polymer composite
The fields such as material, medicine, papermaking, building materials.But there is substantial amounts of oh group on CNF surfaces, it is shown strong polarity
Feature, when the draw ratio of CNF is more than 100, its huge specific surface area is easy to reunite in nonpolar PLA, from
And real enhancing effect cannot be played, and when being strengthened PLA using the CNF of low draw ratio (being less than 100), its mechanical property is carried
Rise very limited.Therefore PLA is strengthened using the CNF of high length-diameter ratio, it is necessary to by the filament of its netted entanglement equably
It is distributed in PLA matrixes, only solves the interface compatibility of agglomeration traits and CNF and PLA of the CNF in plastic substrate,
Real enhancing effect can be played.
The content of the invention
It is susceptible to reunite to solve high length-diameter ratio biomass nano cellulose in the prior art, it is impossible to play real
The defects such as enhancing effect, the present invention provides a kind of high length-diameter ratio nano-cellulose enhanced lactic acid composite material.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
One kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose, its raw material components include：High length-diameter ratio
Nano-cellulose 30-50 parts, ionomer 3-5 parts and PLA 45-67 parts, the number is mass fraction, high length-diameter ratio
The draw ratio of nano-cellulose is more than 100.
Above-mentioned composite does not use the poisonous chemical reagent for having a pollution, is a kind of product of environmental protection.The application will
Nano-cellulose of the draw ratio more than 100 is defined as high length-diameter ratio nano-cellulose.
The above-mentioned interfacial compatibilizer by the use of ionomer as CNF and PLA, its amphipathic chemical constitution is effectively carried
The interface compatibility of CNF/PLA composites high, its structure and performance may further result in the viscous of CNF/PLA Composite Melts
Degree is reduced, so as to improve rheological property.
In order to further improve the interface compatibility of CNF and PLA, it is preferable that ionomer is polymerized for Surlyn sodium ions
Thing or Surlyn zinc ionomers.
Ionomer Surlyn is the copolymer of ethylene-methyl methacrylate, can be from being commercially available on the market.
In order to be able to play more preferable enhancing effect to PLA, it is preferable that the draw ratio of high length-diameter ratio nano-cellulose is
100-1000.Further preferably, a diameter of 50-100nm of high length-diameter ratio nano-cellulose.
The application high length-diameter ratio nano-cellulose prepares raw materials used can select and contains the various of cellulose in the prior art
Raw material, but being conveniently easy to get for raw material, while ensureing the enhancing effect to PLA, it is preferable that prepare high length-diameter ratio Nanowire
It is wood powder, cotton, bamboo fibre or agricultural crop straw that dimension element is raw materials used.
High length-diameter ratio nano-cellulose is specifically prepared as：The hemicellulose and wooden in removal raw material is processed using soda acid
Plain composition, then fibrillation treatment is carried out to CNF aggregations by means such as HCl treatment, mechanical lapping, ultrasonications, obtain final product,
Specific method can refer to prior art.
In order to prepare conveniently, while ensureing the quality of products obtained therefrom, it is preferable that PLA is extrusion or the other poly- breast of injection grade
Granulates.
The preparation method of the enhanced lactic acid composite material of above-mentioned nano-cellulose, including following steps connected in order：
(1) high length-diameter ratio nano-cellulose water slurry of the draw ratio more than 100 is prepared；
(2) PLA is prepared as powder and is added to the aqueous suspension of the high length-diameter ratio nano-cellulose obtained by step (1)
In liquid, after heating stirring, filtering, and will filtering gained solid freeze-drying；
(3) after step (2) resulting material is smashed, with ionomer melt blending, then extrusion molding is obtained final product.
In above-mentioned steps (2), heating stirring is preferably carried out in magnetic force heating stirrer, and it is left that mixing time is preferably 1h
The right side, whipping temp is 75 DEG C -90 DEG C.Melt blending preferably enters in HAAKE Minilab minipool rheometers in step (3)
OK.
Above-mentioned ionomer reduces the viscosity of CNF/PLA Composite Melts during melt blending, improves multiple
The rheological property of condensation material.By the pretreatment in step (2), the problem of reunion is set to have obtained effective solution.
In order to ensure the matter of gained high length-diameter ratio nano-cellulose suspension in the mechanical strength of products obtained therefrom, step (1)
Amount concentration is 0.5%-2%.Further preferably, the mass concentration of the middle gained high length-diameter ratio nano-cellulose suspension of step (1)
It is 1%.
In order to be further ensured that the mechanical strength and heat endurance of products obtained therefrom, it is preferable that in step (3), melt blending
Temperature is 170 DEG C -180 DEG C, and rotating speed is 40-80r/min, and the blending time is 8-10min.Further preferably, in step (3), squeeze
Screw speed is 30-50r/min when going out.Still more preferably, the rotating speed of melt blending is 60r/min, screw speed during extrusion
It is 40r/min.
The NM technology of the present invention is with reference to prior art.
The present invention enhanced lactic acid composite material of high length-diameter ratio nano-cellulose, using high intensity, high thermal stability,
Environment-friendly nano-cellulose strengthens PLA, using physics pretreatment method that the nano-cellulose of high length-diameter ratio is equal
Even to be distributed in nonpolar PLA matrixes, the method for pretreating does not use any chemical reagent, and nontoxic pollution-free is a kind of green
The method for pretreating of environmental protection；The present invention is significantly carried by the use of ionomer as nano-cellulose and the interfacial compatibilizer of PLA
The interface compatibility of nano-cellulose/lactic acid composite material high, at the same reduce nano-cellulose during melt blending/
The viscosity of lactic acid composite material melt, improves the rheological property of composite；The present invention utilizes the Nanowire of high length-diameter ratio
Dimension element strengthens PLA, and fiber is punctured in PLA matrix with three-dimensional netted filament structure, gained composite
Fracture mode is ductile rupture, significantly improves the mechanical strength of existing poly-lactic acid material, especially toughness, while also
Considerably improve the thermal stability of poly-lactic acid material.
Brief description of the drawings
Fig. 1 is the shear rate-viscosity profile of the application CNF/PLA composites；
Fig. 2 is mechanical strength figure (a. bending strengths of the application CNF/PLA composites；B. elastic modelling quantity；C. shock resistance
Toughness)；
Fig. 3 is thermal coefficient of expansion (CTE) figure of the application CNF/PLA composites；
Fig. 4 is SEM sectional drawings (a. examples 1 of the application CNF/PLA composites；B. example 2；C. comparative example 1；D. it is right
Ratio 2；E. example 3；F. example 4；G. comparative example 3；H. comparative example 4).
Specific embodiment
For a better understanding of the present invention, it is with reference to the embodiment content that the present invention is furture elucidated but of the invention
Content is not limited solely to the following examples.
Embodiment 1
(1) CNF is prepared by raw material of absorbent cotton：10g medical absorbent cottons are weighed with electronic balance, tiny piece is torn into
Shape；Take the sodium chlorite (NaClO of the distilled water of 650mL, the glacial acetic acid of 5mL and 6g2) be placed in beaker be well mixed, then will
Be torn into it is tiny bulk absorbent cotton be put into beaker, be placed in magnetic force heating stirrer be heated to 75 DEG C treatment 1h removal it is wooden
Element, is then cleaned to neutrality with distilled water；It is 2% that 650mL mass fractions are added to after being filtered except the absorbent cotton of delignification
KOH solution in be well mixed, at 90 DEG C heating stirring 2h removal hemicellulose, then cleaned to neutrality with distilled water；Again
Fibrillation treatment in the hydrochloric acid solution that 650mL mass fractions are 1% is added to after the absorbent cotton filtering that hemicellulose will be removed, in 80
Heating stirring 2h at DEG C, is then cleaned to neutrality with distilled water, obtains CNF suspension；Finally CNF suspension is poured into grinder
Grinding 20 times, the rotating speed of mill is 1800r/min, the diameter of the CNF of preparation in 50-100nm, the length of individual filaments 10~
Between 50 μm, show the draw ratio of fibril between 100-1000.
(2) by the PLA of 3g, (relative molecular weight is 1 × 105, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s) grind
Powder into 60-80 mesh is added in the absorbent cotton CNF water slurries of 270g (mass concentration 1%), is placed in magnetic force heating and is stirred
Mix and be heated in device 80 DEG C of stirring 1h, then carry out suction filtration with Buchner funnel, the solid mixture that suction filtration is obtained is freezed
Dry (temperature of cold-trap is set to -55 DEG C)；The mixture after freeze-drying is smashed with mixer again, is polymerized with 0.3g sodium ions
Thing (model：Surlyn 8920) it is added to together in HAAKE Minilab minipool rheometers and is blended, blending temperature
Be set as 180 DEG C, rotating speed is 60r/min, the blending time be 10min, last extrusion molding, during extrusion screw speed be 40r/
min。
Comparative example 1
(1) it is identical with step (1) in embodiment 1；
(2) after the absorbent cotton CNF suspension of the gained of embodiment 1 being carried out into suction filtration, freeze-drying, the PLA of 2.7g and 3g is taken
(relative molecular weight is 1 × 10 to particle5, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s), 0.3g sodium ion polymer (types
Number：Surlyn 8920) it is added to together in HAAKE Minilab minipool rheometers and is blended, temperature is set as 180
DEG C, rotating speed is 60r/min, the blending time be 10min, last extrusion molding, during extrusion screw speed be 40r/min.
Comparative example 2
(1) it is identical with step (1) in embodiment 1；
(2) by the PLA of 3g, (relative molecular weight is 1 × 105, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s) grind
Powder into 60-80 mesh is added in the absorbent cotton CNF water slurries of 270g (mass concentration 1%), is placed in magnetic force heating and is stirred
Heating stirring 1h in device is mixed, whipping temp is 80 DEG C, then carries out suction filtration with Buchner funnel, the solid mixture that suction filtration is obtained
Carry out freeze-drying (temperature of cold-trap is set to -55 DEG C)；The mixture after freeze-drying is smashed with mixer again, is passed with 0.3g
System coupling agent maleic anhydride grafted polyethylene (MAPE, particle, grafting rate 0.8%, purchased from Nanjing De Ba Chemical Co., Ltd.s) one
Rise to be added in HAAKE Minilab minipool rheometers and be blended, blending temperature is set as 180 DEG C, and rotating speed is 60r/
Min, the blending time be 10min, last extrusion molding, during extrusion screw speed be 40r/min.
Embodiment 2
(1) it is identical with step (1) in embodiment 1；
(2) by the PLA powder of 2.8g, (relative molecular weight is 1 × 105, extrusion grade, purchased from the Shanghai easily limited public affairs of raw industry
Department) (60-80 mesh) is added in the absorbent cotton CNF water slurries of 300g (mass concentration 1%), is placed in magnetic force heating stirrer
In be heated to 75 DEG C stirring 1h, then carry out suction filtration with Buchner funnel, the solid mixture that suction filtration is obtained carries out freeze-drying
(temperature of cold-trap is set to -55 DEG C)；The mixture after freeze-drying is smashed with mixer again, with 0.2g zinc ionomers
(model：Surlyn 9120) it is added to together in HAAKE Minilab minipool rheometers and is blended, temperature is set as
180 DEG C, rotating speed is 60r/min, the blending time be 8min, last extrusion molding, during extrusion screw speed be 40r/min.
Embodiment 3
(1) CNF is prepared by raw material of Poplar Powder：10g Poplar Powders are weighed with electronic balance, is put into Soxhlet extraction device and is used benzene
Ethanol solution carries out filtering extracting to it to remove impurity therein, wherein, the volume ratio of toluene and ethanol solution is 2:1, take out
Temperature raising degree is 80~90 DEG C, and extraction times are 5~7h, after extracting terminates, wood powder are cleaned using ethanol solution, after filtering
It is placed in and dries at room temperature, is taken after being completely dried；The wood powder of above-mentioned gained is weighed into 8g and is put into the distilled water that fills 650mL
In beaker, and add the glacial acetic acid of 5mL and the sodium chlorite (NaClO2) of 6g to be well mixed, beaker is placed in magnetic force heating stirring
75 DEG C of stirring 6h removal lignin are heated in device, a 5mL glacial acetic acid and 6g sodium chlorites are added every 1h during heating,
After treatment terminates, wood powder is cleaned to neutrality with distilled water；650mL matter will be added to after the foregoing wood powder filtering except delignification
Amount concentration removes hemicellulose to be well mixed in the KOH solution of 2wt%, heating stirring 2h at being 90 DEG C in temperature, treatment knot
Shu Hou, is cleaned to neutrality with distilled water；650mL matter is added to after being filtered except the cotton wood cellulose of delignification and hemicellulose
Amount concentration be 1% hydrochloric acid solution in be well mixed, the heating stirring 2h at 80 DEG C, after treatment terminates, cleaned with distilled water to
It is neutral；Finally suspension is poured into grinder and is ground 20 times, the rotating speed of mill is 1800r/min, and the diameter of the CNF of preparation exists
50-100nm, the length of individual filaments shows the draw ratio of fibril between 100-1000 between 10~50 μm.
(2) by PLA (relative molecular weight is 1 × 105, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s) mill of 2.7g
It is broken into the poplar CNF water slurries the step of powder of 60-80 mesh is added to 300g (mass concentration 1%) obtained by (1), juxtaposition
90 DEG C of stirring 1h are heated in magnetic force heating stirrer, then suction filtration is carried out with Buchner funnel, the solid that suction filtration is obtained is mixed
Compound carries out freeze-drying (temperature of cold-trap is set to -55 DEG C).The mixture after freeze-drying is smashed with mixer again, with
0.3g sodium ion polymer (models：Surlyn 8920) it is added to together in HAAKE Minilab minipool rheometers and carries out
Blending, temperature is set as 180 DEG C, and rotating speed is 60r/min, and the blending time is 10min, last extrusion molding, screw rod turn during extrusion
Speed is 40r/min.
Comparative example 3
(1) it is identical with step (1) in embodiment 3；
(2) step (1) gained Poplar Powder CNF suspension taken out, after freeze-drying, take the PLA (average moleculars of 3g and 2.7g
It is 1 × 105 to measure, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s) particle, 0.3g sodium ion polymer (models：Surlyn
8920) it is added to together in HAAKE Minilab minipool rheometers and is blended, temperature is set as 180 DEG C, and rotating speed is
60r/min, the blending time be 10min, last extrusion molding, during extrusion screw speed be 40r/min.
Comparative example 4
(1) it is identical with step (1) in embodiment 3；
(2) by PLA (relative molecular weight is 1 × 105, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s) powder of 2.7g
Last (60-80 mesh) is added in the Poplar Powder CNF water slurries of 300g (mass concentration 1%), is placed in magnetic force heating stirrer
In be heated to 90 DEG C stirring 1h, then carry out suction filtration with Buchner funnel, the solid mixture that suction filtration is obtained carries out freeze-drying
(temperature of cold-trap is set to -55 DEG C)；The mixture after freeze-drying is smashed with mixer again, it is poly- with the grafting of 0.3g maleic anhydrides
Ethene (MAPE) is blended in being added to HAAKE Minilab minipool rheometers together, and temperature is set as 180 DEG C, is turned
Speed be 60r/min, the blending time be 10min, last extrusion molding, during extrusion screw speed be 40r/min.
Embodiment 4
(1) it is identical with step (1) in embodiment 3；
(2) by the PLA of 3.4g, (relative molecular weight is 1 × 105, extrusion grade, purchased from Shanghai Yi Sheng Industrial Co., Ltd.s) and powder
Last (60-80 mesh) is added in the Poplar Powder CNF water slurries of 240g (mass concentration 1%), is placed in magnetic force heating stirrer
In be heated to 85 DEG C stirring 1h, then carry out suction filtration with Buchner funnel, the solid mixture that suction filtration is obtained carries out freeze-drying
(temperature of cold-trap is set to -55 DEG C)；The mixture after freeze-drying is smashed with mixer again, with 0.2g zinc ionomers
(model：Surlyn 9120) it is added to together in HAAKE Minilab minipool rheometers and is blended, temperature is set as
180 DEG C, rotating speed is 60r/min, the blending time be 8min, last extrusion molding, during extrusion screw speed be 40r/min.
Performance test methods：
(1) rheology testing：
With the capillary of HAAKE Minilab minipool rheometer tests the various embodiments described above gained Composite Melt
Rheological behavior, temperature is set as 180 DEG C, and using co-rotating conical twin-screw, speed setting is from 10rpm to 100rpm.
(2) Mechanics Performance Testing：
The bending strength and elasticity of products obtained therefrom test specimen in above-mentioned embodiment are tested according to standard ASTM D 790-2010
Modulus, the toughness of test specimen is tested according to standard ASTM D 256-2010, and 6 zero defect test specimens are selected in test every time.
(3) thermal coefficient of expansion (CTE) test：
The CTE value varied with temperature using thermomechanical analyzer (TMA) test piece lengths direction, temperature range is -20
DEG C~110 DEG C, rate temperature change is 5 DEG C/min, and loaded load is 1N, and sample dimensions are 15mm × 5mm × 1mm.
(4) SEM (SEM) test：
The cross-section morphology of sample is observed using SEM (SEM).
Result and analysis：
(1) rheological property
Fig. 1 is the rheological property curve of the CNF/PLA composites of the ionomer and MAPE that add same amount, from
As can be seen that CNF/PLA Composite Melts viscosity is reduced with the increase of shear rate in figure, show to add ionic polymerization
The CNF/PLA composites of thing and MAPE are all pseudoplastic fluid, show the effect of " shear shinning ".May be used also from figure
Go out, no matter raw material is absorbent cotton or Poplar Powder, and the CNF/PLA Composite Melts viscosity for adding ionomer will be less than
The composite of MAPE is added, shows that ionomer can more improve the mobile performance of CNF/PLA composites, reduce melt
Frictional resistance during flowing between CNF and PLA, so as to reduce the viscosity of melt, improves the processing characteristics of composite.
(2) mechanical property
Fig. 2 is bending strength, elastic modelling quantity and the toughness of CNF/PLA composites.It can be seen that nothing
It is absorbent cotton or Poplar Powder by the raw material of CNF, the bending resistance of the CNF/PLA composites prepared using physics pretreatment method is strong
Degree, elastic modelling quantity and toughness are all significantly larger than pure PLA, show that CNF serves expected enhancing effect, when CNF's
When addition is 50%, the bending strength of absorbent cotton CNF/PLA composites (example 2), elastic modelling quantity and toughness point
Not Wei 46.5MPa, 3695MPa and 53.8J/m, improve 218.5%, 136.6% and 617.3% than pure PLA；Poplar CNF/
The bending strength of PLA composites (example 3), elastic modelling quantity and toughness have been respectively increased 230.1% than pure PLA,
149.2% and 676%.From this figure it can be seen that the mechanics of the CNF/PLA composites prepared using physics pretreatment method is strong
Degree will be significantly larger than composite prepared by direct dry pigmentation, when the addition of CNF is 45%, using physics pretreatment legal system
The bending strength of standby absorbent cotton CNF/PLA composites (example 1), elastic modelling quantity and toughness are respectively 39.8MPa,
3288MPa and 45.2J/m, absorbent cotton CNF/PLA's composites (comparative example 1) that Billy is prepared with direct dry pigmentation
21.4MPa, 1869MPa and 10.2J/m, have been respectively increased 85.9%, 75.9% and 343.1%, show that physics pretreatment method rises
More preferable enhancing effect is arrived.When 5% sodium ion polymer is added, absorbent cotton CNF/PLA's composites (example 1) is anti-
Curved intensity, elastic modelling quantity and toughness are respectively 39.8MPa, 3288MPa and 45.2J/m, than addition same amount MAPE
Absorbent cotton CNF/PLA composites (comparative example 2) improve 6.1%, -1.1% and 38.7%；When the sodium ion of addition 5%
During polymer, the bending strength of poplar CNF/PLA composites (example 3), elastic modelling quantity and toughness are respectively
48.2MPa, 3892MPa and 58.2J/m, poplar CNF/PLA composites (comparative example 4) than addition same amount MAPE are improved
- 0.6%, -5.1% and 58.6%, it can be found that the bending strength of composite after addition ionomer with add phase
Composite with the MAPE of content is suitable, shows that ionomer serves the effect of coupling agent, improves CNF's and PLA
Interface compatibility, the toughness for particularly adding the composite after ionomer is greatly improved, and explanation can
Used with instead of traditional coupling agent MAPE.But because ionomer is thermoplastic elastomer body, the elastic modelling quantity of itself
Relatively low, the elastic modelling quantity for thus resulting in CNF/PLA composites decreases.
(3) thermal coefficient of expansion (CTE)
Fig. 3 is CTE value of the CNF/PLA composites in the range of -20 DEG C~110 DEG C.CNF has very low thermal expansion system
Number (0.1ppm/k), and unbodied PLA molecular chain orientations are poor, molecules align is out of order, and intermolecular distance is larger, to temperature
Change is more sensitive, and CNF and PLA can be significantly reduced the thermal coefficient of expansion of pure PLA after compound, improves the heat endurance of PLA；
As can be seen from Figure 3, after 50% CNF is added, the absorbent cotton/PLA composites (example 2) prepared using physics pretreatment method
CTE is 45.2ppm/k, and 74.9% is reduced than the 180ppm/k of pure PLA, the CTE of poplar/PLA composites (example 3) for
40.7ppm/k, 77.4% is reduced than pure PLA, because fibril is staggered into tridimensional network with fibril so that PLA bases
The resistance increase of body flowing, strand is deformed upon and greatly limited, so as to serve the effect of limitation thermal expansion.From figure also
As can be seen that comparing physics pretreatment method, the CTE value of the CNF/PLA composites prepared using direct dry pigmentation is then had substantially
Rising, using direct dry pigmentation prepare absorbent cotton CNF/PLA composites CTE value Billy with physics pretreatment method prepare
The CTE value of composite improve 128.8%, and utilize the CTE of poplar CNF/PLA composites prepared by direct dry pigmentation
Value Billy improves 164.1% with composite prepared by physics pretreatment method, shows to achieve CNF using physics pretreatment method
Dispersed effect in PLA matrixes.
(4) SEM (SEM)
Figure 4, it is seen that the CNF/PLA composites (scheming a, b, d, e, f, h) prepared using physics pretreatment method
Section have substantial amounts of netted filament, be dispersed in the section of composite these filament dense uniforms, reached to CNF
Expected dispersion effect, the fracture mode of PLA material is no longer brittle fracture, and is changed into ductile rupture.And pass through directly dry-mixed
The section of CNF/PLA composites prepared by method can clearly be seen that the fiber aggregate of CNF, these fiber aggregates Yin Qibiao
The strong Hyarogen-bonding in face cannot be dispersed in PLA matrixes, so as to enhancing effect (figure c, g) cannot be played.From figure
It can also be seen that the size and pattern of the CNF prepared using different biomass materials are all made a big difference, using absorbent cotton CNF
The netted filament that the section of the composite of preparation does not have high length-diameter ratio is distributed, but is present in substantial amounts of fibril aggregation multiple
The section (figure a, b, d) of condensation material, shows that the draw ratio of poplar CNF wants a little higher than absorbent cotton CNF (figure e, f, h), can more have
Stress loading is delivered to PLA by effect ground, has mechanical strength higher so as to cause poplar CNF/PLA composites.From figure
It is also found that the cross-section morphology of the composite of the CNF/PLA composites of addition ionomer and MAPE has no substantially
Difference, show the interfacial compatibilizer (figure d, h) that ionomer can replace MAPE as both CNF/PLA.
Claims (8)
1. a kind of with the enhanced lactic acid composite material of high length-diameter ratio nano-cellulose, it is characterised in that：Its raw material components includes：
30-50 parts of high length-diameter ratio nano-cellulose, ionomer 3-5 parts and PLA 45-67 parts, the number is mass fraction,
The draw ratio of high length-diameter ratio nano-cellulose is more than 100；
Ionomer is Surlyn sodium ions polymer or Surlyn zinc ionomers；
The preparation method of the enhanced lactic acid composite material of above-mentioned nano-cellulose, including following steps connected in order：
(1) high length-diameter ratio nano-cellulose water slurry of the draw ratio more than 100 is prepared；
(2) in the high length-diameter ratio nano-cellulose water slurry that PLA is prepared as powder and is added to obtained by step (1), plus
After thermal agitation, filtering, and will filtering gained solid freeze-drying；
(3) after step (2) resulting material is smashed, with ionomer melt blending, then extrusion molding is obtained final product.
2. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1, it is characterised in that：High length-diameter ratio nanometer
The draw ratio of cellulose is 100-1000.
3. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1 or 2, it is characterised in that：High length-diameter ratio
A diameter of 50-100nm of nano-cellulose.
4. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1 or 2, it is characterised in that：Prepare high long
It is wood powder, cotton, bamboo fibre or agricultural crop straw that footpath is more raw materials used than nano-cellulose.
5. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1 or 2, it is characterised in that：PLA is
Extrusion or the other particles of polylactic acid of injection grade.
6. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1 or 2, it is characterised in that：In step (1)
The mass concentration of gained high length-diameter ratio nano-cellulose suspension is 0.5%-2%.
7. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1 or 2, it is characterised in that：Step (3)
In, the temperature of melt blending is 170 DEG C -180 DEG C, and rotating speed is 40-80r/min, and the blending time is 8-10min.
8. the enhanced lactic acid composite material of nano-cellulose as claimed in claim 1 or 2, it is characterised in that：Step (3)
In, screw speed is 30-50r/min during extrusion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510369094.4A CN104910422B (en) | 2015-06-29 | 2015-06-29 | One kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose and preparation method thereof |
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| CN201510369094.4A CN104910422B (en) | 2015-06-29 | 2015-06-29 | One kind enhanced lactic acid composite material of high length-diameter ratio nano-cellulose and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106543757A (en) * | 2016-10-11 | 2017-03-29 | 洛阳鼎威材料科技有限公司 | A kind of Plant fiber's enhancing hydrophobic polymer composite, and preparation method thereof |
| CN108003645A (en) * | 2017-12-28 | 2018-05-08 | 武汉华丽环保科技有限公司 | A kind of complete biodegradable stalk injection-moulded plastic and preparation method thereof |
| CN108250696A (en) * | 2017-12-28 | 2018-07-06 | 武汉华丽环保科技有限公司 | A kind of cellulose complete biodegradable construct blow-molded and preparation method thereof |
| CN108486676B (en) * | 2018-04-18 | 2021-01-22 | 济南圣泉集团股份有限公司 | Nano cellulose modified acrylic fiber, preparation method and application thereof |
| CN108721702B (en) * | 2018-06-29 | 2021-06-29 | 江西理工大学 | Preparation method of magnesium/L-polylactic acid composite bone scaffold |
| CN109880180B (en) * | 2019-03-13 | 2021-03-02 | 广州谱睿汀新材料科技有限公司 | Nano-cellulose/cellulose compound, reinforced polylactic acid 3D printing material and preparation method thereof |
| CN112280266A (en) * | 2020-11-02 | 2021-01-29 | 天津科技大学 | Synchronous preparation process of reactive cellulose nano-fibril/polylactic acid composite material |
| CN113072802B (en) * | 2021-04-02 | 2024-01-09 | 湖南省林业科学院 | Preparation method of high-length-diameter-ratio bamboo cellulose nanofiber reinforced polylactic acid composite material |
| CN116355373A (en) * | 2023-04-20 | 2023-06-30 | 四川大学 | Polylactic acid-based composite material and preparation method thereof |
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