CN103992493B - A kind of modified ramie nano-cellulose and the preparation method of PLA laminated film - Google Patents
A kind of modified ramie nano-cellulose and the preparation method of PLA laminated film Download PDFInfo
- Publication number
- CN103992493B CN103992493B CN201410217621.5A CN201410217621A CN103992493B CN 103992493 B CN103992493 B CN 103992493B CN 201410217621 A CN201410217621 A CN 201410217621A CN 103992493 B CN103992493 B CN 103992493B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- nano
- ramie
- pla
- laminated film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides the preparation method of a kind of modified ramie nano-cellulose and PLA laminated film, with ramie nano-cellulose and two kinds of biomass resources of polylactic resin as raw material, utilize hardwood xylan that ramie nano-cellulose is carried out hydrophobic modification, PLA and modified ramie nano-cellulose are dissolved in organic solvent, the method using solvent cast, liquid of blends described above being cast slowly is poured on polystyrene moulding, putting into fume hood at room temperature makes solvent naturally volatilize, final curing shaping prepares modified ramie nano-cellulose and PLA laminated film.The method that the present invention provides is simple to operate, production cost is low, material therefor is all degradable biomass material, cheap and easy to get, the film prepared has the highest hot strength and elongation at break, simultaneously good air permeability, biodegradable, steady quality, has good pliability and biocompatibility, can be used for the fields such as packaging material for food, agricultural film and industrial product packaging film.
Description
Technical field
The present invention relates to the preparation method of a kind of modified ramie nano-cellulose and PLA laminated film, belonging to can
The preparation of degradation biological matter thin-film material and nano composite material technical field.
Background technology
Along with progress and the enhancing of environmental protection ideas of technology, natural plant fibre system compound with biodegradable plastics
The exploitation application of standby living beings Green Composites is increasingly subject to the concern of people, and is increasingly becoming composite
The inexorable trend of development and study hotspot.PLA (PLA) is with lactic acid for gathering that primary raw material polymerization obtains
Compound, raw material sources fully and can regenerate, and catabolite is carbon dioxide and water, to air and soil not
Toxic action can be produced, be a kind of multiduty ecological, environmental protective macromolecular material, there is excellent thermomechanical property
And optical property, there is excellent tensile strength and extensibility simultaneously, can use multiple according to different demands
Mode is processed, and makes various types of product.Through forming method systems such as blowing, calendering, solvent volatilizations
The polylactic acid film obtained, has good biocompatibility and good gas permeability and antibacterial anti-mildew characteristic, at food
The aspects such as product packaging film, agricultural film can replace the difficult degradation such as polypropylene, polyvinyl chloride " white pollution " to mould
The use of material film, has broad application prospects.
But, due to the weakness on this body structure of PLA, cause it polylactic acid film intensity is low, fragility is high,
Poor toughness, in order to improve the mechanical property of polylactic acid film, increases its molecule chain flexibility and toughness, can adopt
With the abundant string of nature as the reinforcement of lactic acid composite material.That extracts from ramee receives
Rice cellulose, has high specific surface area, high degree of crystallinity, low thermal coefficient of expansion and good mechanical property
Can, it is possible to strengthen intensity and the hardness of composite, improve its physical and mechanical property.But, due to natural
String has stronger polarity and hydrophily so that it is and interface adhesion between non-polar resin is poor, can lead
Cause its function strengthening phase significantly to decline.Therefore nano-cellulose is before being introduced, it will be carried out hydrophobization
Modification, reduces hydrophily and polarity, improves the interface compatibility between hydrophobic resin matrix.Hardwood wood gathers
Sugar is the one in xylan, belongs to the hemicellulose components in plant cell, is that nature content is the abundantest
Polysaccharide.Hardwood xylan presented in O-acetyl group-4-O-methyl-glucuronic acid-xylan, this
Class xylan is how highly acetylated in C-3 site, and a large amount of acetyl group and hydroxyl are present in surface, easily with nanometer
Oxygen atom in cellulose plays bonding action, is connected with the hydrogen bond of cellulose simultaneously, forms stable stereoscopic graticule
Shape structure.Containing acetyl group in hardwood xylan, acetyl group has hydrophobicity, makes whole by bridge joint effect
Cellulose macromolecule chain has hydrophobic performance, thus the mechanical strength of nano-cellulose, flexility and hydrophobic
Performance has greatly improved.
Composite material film preparation technology has injection, extrusion, hot pressing, dipping, laminate layer, is blended and mediates and molten
The multiple methods such as agent casting.Solvent cast therein (solvent casting), refers to select suitable solvent to incite somebody to action
Polymer dissolves and prepares casting liquid, will casting drop on substrate or surface plate, fume hood allows solvent room temperature
Under the conditions of naturally volatilization, final curing film forming.Solvent casting method masking technique is simple to operate efficiently, membrance casting condition
Gentleness, can control the thickness of film forming according to the casting concentration of liquid, consumption and substrate area.Prepare is thin simultaneously
Between film, closely, film finished product internal stress is little, has good mechanical strength and mechanical property in connection, has extensively
Purposes.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of with ramie nano-cellulose and polylactic resin two kinds
Biomass resource is raw material, makes the side of the composite material film with good pliability and biocompatibility
Method.
In order to solve above-mentioned technical problem, the technical scheme is that a kind of modified ramie nano-cellulose of offer
Preparation method with PLA laminated film, it is characterised in that: the method is made up of following 3 steps:
Step 1: ramie nano-cellulose and PLA pretreatment
Ramie nano-cellulose is put into equilibrium water conten in the container with sealing ring, measures ramie nano-cellulose
Regain；Weigh ramie nano-cellulose quality, calculate ramie nano-cellulose dry weight according to regain；?
Ramie nano-cellulose adds distilled water, makes ramie nano-cellulose fully soak by distilled water immersion molten
Swollen；
Being put into by polylactic resin in baking oven and dry, the polylactic resin dried completely by moisture is dissolved in organic solvent
In, stir at a set temperature, make polylactic resin be completely dissolved；
Step 2: the hydrophobic modification of ramie nano-cellulose
Hardwood xylan is put in a container, add distilled water and heat, making hardwood xylan fully dissolve；
Ramie nano-cellulose after soaking wetting joins in this hardwood xylan solution, puts in ultrasonic wave and divides
Dissipate, and obtain uniform and stable modified ramie nano-cellulose suspension by mechanical agitation；By prepared mixing
Thing is centrifuged layering, is leached by supernatant liquor, and the ramie nano-cellulose suspension after remaining concentration is put into
In vacuum freeze drier, and liquid-nitrogen freeze drying is used to be molded, by the ramie nanofiber after hydrophobic modification
Element powder is put into refrigerating chamber and is stored；
Step 3: prepared by laminated film
Modified ramie nanofiber powder is mixed with the organic solvent dissolved with PLA, heating, fully stir
Mix and ultrasonic vibration, prepare casting liquid；This casting liquid is poured on polystyrene moulding, puts in vent cabinet
At room temperature solvent flashing, places in vacuum drying oven and is dried to remove residual solvent, forms one layer in template
Film, is modified ramie nano-cellulose and the PLA laminated film of required preparation, finally takes off film and seal guarantor
Deposit.
Preferably, in described step 1, the amount of the distilled water added in ramie nano-cellulose is: make ramie
Nano-cellulose solid mass percent concentration in distilled water is 0.5%～3%；The distilled water immersion time is
12～48h.
Preferably, in described step 1, the drying temperature of polylactic resin is 40～80 DEG C, and drying time is
12～60h；The design temperature of stirring is 30～60 DEG C, and mixing time is 2～6h.
Preferably, in described step 1, the organic solvent dissolving polylactic resin is oxolane, chloroform, two
Chloromethanes, acetone, benzene, toluene, formic acid, dioxane, one or more in tetrachloromethane.
Preferably, in described step 2, hardwood xylan solution temperature is 60～95 DEG C, and the heat time is 0.5～3h；
Hardwood xylan consumption is the 5%～20% of ramie nano-cellulose consumption.
Preferably, in described step 2, the frequency of ultrasonic disperse is 20～40kHz, the output work of ultrasonic disperse
Rate is 100～300W；Carrying out mechanical agitation at a temperature of 50～90 DEG C, mechanical agitation speed is
800～1200rpm, the mechanical agitation time is 1～4h.
Preferably, in described step 2, it is centrifuged being layered by mixture in container by the method for centrifuge washing,
Centrifuge speed is 6000～12000rpm, and centrifugal number of times is 3～6 times；Use the temperature of liquid-nitrogen freeze drying shaping
Degree is-40～-60 DEG C, and pressure is 10～60Pa, and the time is 4～10h.
Preferably, in described step 3, by organic with dissolved with PLA of modified ramie nanofiber powder
The mixed heating-up temperature of solvent is 50～90 DEG C, and the heat time is 30～120min, and mechanical agitation speed is
1000～1400rpm, ultrasonic vibration frequency is 20～40kHz, and the ultrasonic vibration time is 30～60min.
Preferably, in described step 3, in the casting liquid prepared, PLA mass fraction is 90%～99%, ramie
The mass fraction of fiber crops nano-cellulose is 1%～10%；The amount of the casting liquid being poured on polystyrene moulding is
5～40ml, polystyrene moulding area is 40～120cm2。
Preferably, in described step 3, the time in vent cabinet of putting into is 12～48h；Vacuum drying oven is dried
Temperature is 40～80 DEG C, and drying time is 12～36h.
The method that the present invention provides overcomes the deficiencies in the prior art, and simple to operate, production cost is low, Ke Yifen
The not disengagement area of the concentration and template by controlling casting liquid controls film thickness and evaporation rate of solvent, institute
Extensive with material and modifier source, environmental protection, prepared film is eco-friendly, biodegradable,
Steady quality simultaneously, has good pliability and biocompatibility, can be used for film vacuum after drying eating
The fields such as product packaging material, agricultural film and industrial product packaging film.
Detailed description of the invention
For making the present invention become apparent, hereby with several preferred embodiments, it is described in detail below.
Embodiment 1
A kind of modified ramie nano-cellulose is as follows with the preparation method of PLA laminated film:
Ramie nano-cellulose is put into equilibrium water conten in the container with sealing ring, measures ramie nano-cellulose
Regain be 8.7%.Weighing ramie nano-cellulose quality 22.10g, calculating its dry weight according to regain is
20.18g.Adding a certain amount of distilled water, making ramie nano-cellulose mass percent concentration is 3%, soaks
24h, makes ramie nano-cellulose fully soak swelling.
Polylactic resin (Nature Works company of the U.S., 2002D model) is put in 40 DEG C of baking ovens and dry
Dry 12h, makes moisture dry completely.Weighed polylactic resin is dissolved in chloroform solvent, stirs at 30 DEG C
Mix 2h, make polylactic resin be completely dissolved.
1.01g hardwood xylan (for the 5% of ramie nano-cellulose consumption) is put in a container, adds
Distilled water heats 0.5h at 60 DEG C, makes hardwood xylan fully dissolve.The ramie nanometer after soaking will be soaked
Cellulose joins in hardwood xylan solution, put into supersonic frequency be 20kHz, ultrasonic power output be 100W
Ultrasonic wave in disperse, at 50 DEG C, stir 1h with the speed mechanical of 800rpm, finally obtain uniform and stable
Modified ramie nano-cellulose suspension.With the centrifuge that rotating speed is 6000rpm, mixture is centrifuged 3 times and makes it
Layering, leaches supernatant liquor, and the nano-cellulose suspension after concentration is put in vacuum freeze drier, sample
Product use liquid nitrogen quick freeze drying and moulding 4h under-40 DEG C and 10Pa pressure condition, after hydrophobic modification
Nano-cellulose powder is put into refrigerating chamber and is stored.
Modified ramie nanofiber powder is mixed with the organic solvent dissolved with PLA, poly-breast in mixture
Acid mass fraction is 90%, and the mass fraction of ramie nano-cellulose is 10%, and mixture heats at 50 DEG C
30min, is sufficiently stirred for the speed of 1000rpm, shakes 30min in the ultrasonic wave that supersonic frequency is 20kHz
Prepare casting liquid.Above-mentioned 5ml blend casting liquid is slowly poured over area is 40cm2Polystyrene moulding
On, put in vent cabinet at room temperature slow evaporation 12h, make solvent volatilize, place into the vacuum drying oven of 40 DEG C
In be dried 12h to remove residual solvent, in template formation the smooth atresia of layer of surface, the film of compact structure,
Finally take off film and seal preservation.
The modified ramie nano-cellulose prepared below by the experimental verification present invention and PLA laminated film, ramie
Fiber crops nano-cellulose and PLA laminated film, the physical and mechanical properties of pure polylactic acid film.Use spiral micrometer
(Stanley company of the U.S.) measures the thickness of film, and 5 the diverse location measurements choosing every film ask flat
Average.With hot strength and the extension at break of omnipotent mechanics tester (American I nstron company) testing film
Rate, makes long 70mm, the rectangle of wide 10mm by film, arranges spacing for 25mm, stretching of test machine
Speed is 10mm/min, and each sample carries out 5 tests and averages.The film of preparation is cut into 20mm
The square of × 20mm, pours the garden soil of 8cm height in beaker into and to add 15ml concentration is 10g/L
Nitrogenous fertilizer (urea) solution.Film dried in vacuum drying chamber and weighs, imbedding beaker soil, every
Within 7 days, sampling first drying is weighed, and represents that its soil buries palliating degradation degree with weight-loss ratio.Water vapor permeation rate tester (in
Blue streak company of state) test water vapour permeability (WVTR), banana measuring instrument (U.S. Modern
Controls company) test OTR oxygen transmission rate.The physical and mechanical properties contrast of three kinds of films is as shown in table 1.
Pure polylactic acid film and PLA laminated film physical and mechanical properties contrast test result in table 1 embodiment 1
As can be seen from Table 1, in three kinds of films, performance most preferably modified ramie nano-cellulose/PLA is multiple
Close film, next to that ramie nano-cellulose/PLA laminated film.The thickness difference of three kinds of films is little,
The addition of modified ramie nano-cellulose can be obviously enhanced the mechanical property of polylactic acid film, hot strength from
29.8MPa increases to 52.6MPa, and elongation at break increases to 27.4% from 5.9%, and laminated film toughness has bright
Aobvious raising.The addition of modified ramie nano-cellulose simultaneously also can significantly improve the degraded speed of PLA laminated film
Spending, the degradable time of PLA laminated film can be kept to 181 days from 293 days.The modified ramie of preparation is received
Rice cellulose and PLA laminated film good air permeability, water vapour permeability is from 217g/ (m224h) carry
High to 523g/ (m224h), OTR oxygen transmission rate is from 320cm3/(m2D) 476cm is brought up to3/(m2·d)。
Embodiment 2
A kind of modified ramie nano-cellulose is as follows with the preparation method of PLA laminated film:
Ramie nano-cellulose is put into equilibrium water conten in the container with sealing ring, measures ramie nano-cellulose
Regain be 8.8%.Weighing ramie nano-cellulose quality 21.40g, calculating its dry weight according to regain is
19.52g.Adding a certain amount of distilled water, making ramie nano-cellulose mass percent concentration is 0.5%, soaks
48h, makes ramie nano-cellulose fully soak swelling.
Polylactic resin (Nature Works company of the U.S., 2002D model) is put in 80 DEG C of baking ovens and dry
Dry 60h, makes moisture dry completely.Weighed polylactic resin is dissolved in tetrahydrofuran solvent, at 60 DEG C
Lower stirring 6h, makes polylactic resin be completely dissolved.
4.28g hardwood xylan (for the 20% of ramie nano-cellulose consumption) is put in a container, adds
Distilled water heats 3h at 95 DEG C, makes hardwood xylan fully dissolve.The ramie Nanowire after soaking will be soaked
Dimension element join in hardwood xylan solution, put into supersonic frequency be 40kHz, ultrasonic power output be 300W
Ultrasonic wave in disperse, at 90 DEG C, stir 4h with the speed mechanical of 1200rpm, finally obtain uniform and stable
Modified ramie nano-cellulose suspension.With the centrifuge that rotating speed is 12000rpm, mixture is centrifuged 6 times
Making it be layered, leached by supernatant liquor, the nano-cellulose suspension after concentration is put in vacuum freeze drier,
Sample uses liquid nitrogen quick freeze drying and moulding 10h under-60 DEG C and 60Pa pressure condition, by hydrophobic modification
After nano-cellulose powder put into refrigerating chamber store.
Modified ramie nanofiber powder is mixed with the organic solvent dissolved with PLA, poly-breast in mixture
Acid mass fraction is 99%, and the mass fraction of ramie nano-cellulose is 1%, and mixture heats at 90 DEG C
120min, is sufficiently stirred for the speed of 1400rpm, shakes 60min in the ultrasonic wave that supersonic frequency is 40kHz
Prepare casting liquid.Above-mentioned 40ml blend casting liquid is slowly poured over area is 120cm2Polystyrene mould
On plate, putting in vent cabinet at room temperature slow evaporation 48h, make solvent volatilize, the vacuum placing into 80 DEG C is dried
In case be dried 36h to remove residual solvent, in template formation the smooth atresia of layer of surface, compact structure thin
Film, finally takes off film and seals preservation.
The modified ramie nano-cellulose prepared below by the experimental verification present invention and PLA laminated film, ramie
Fiber crops nano-cellulose and PLA laminated film, the physical and mechanical properties of pure polylactic acid film.Use spiral micrometer
(Stanley company of the U.S.) measures the thickness of film, and 5 the diverse location measurements choosing every film ask flat
Average.With hot strength and the extension at break of omnipotent mechanics tester (American I nstron company) testing film
Rate, makes long 70mm, the rectangle of wide 10mm by film, arranges spacing for 25mm, stretching of test machine
Speed is 10mm/min, and each sample carries out 5 tests and averages.The film of preparation is cut into 20mm
The square of × 20mm, pours the garden soil of 8cm height in beaker into and to add 15ml concentration is 10g/L
Nitrogenous fertilizer (urea) solution.Film dried in vacuum drying chamber and weighs, imbedding beaker soil, every
Within 7 days, sampling first drying is weighed, and represents that its soil buries palliating degradation degree with weight-loss ratio.Water vapor permeation rate tester (in
Blue streak company of state) test water vapour permeability (WVTR), banana measuring instrument (U.S. Modern
Controls company) test OTR oxygen transmission rate.The physical and mechanical properties contrast of three kinds of films is as shown in table 2.
Pure polylactic acid film and PLA laminated film physical and mechanical properties contrast test result in table 2 embodiment 2
As can be seen from Table 2, in three kinds of films, performance most preferably modified ramie nano-cellulose/PLA is multiple
Close film, next to that ramie nano-cellulose/PLA laminated film.The thickness difference of three kinds of films is little,
The addition of modified ramie nano-cellulose can be obviously enhanced the mechanical property of polylactic acid film, hot strength from
28.0MPa increases to 53.5MPa, and elongation at break increases to 28.0% from 6.1%, and laminated film toughness has bright
Aobvious raising.The addition of modified ramie nano-cellulose simultaneously also can significantly improve the degraded speed of PLA laminated film
Spending, the degradable time of PLA laminated film can be kept to 184 days from 296 days.The modified ramie of preparation is received
Rice cellulose and PLA laminated film good air permeability, water vapour permeability is from 202g/ (m224h) carry
High to 524g/ (m224h), OTR oxygen transmission rate is from 330cm3/(m2D) 482cm is brought up to3/(m2·d)。
Embodiment 3
A kind of modified ramie nano-cellulose is as follows with the preparation method of PLA laminated film:
Ramie nano-cellulose is put into equilibrium water conten in the container with sealing ring, measures ramie nano-cellulose
Regain be 9.0%.Weighing ramie nano-cellulose quality 22.00g, calculating its dry weight according to regain is
20.02g.Adding a certain amount of distilled water, making ramie nano-cellulose mass percent concentration is 1.5%, soaks
12h, makes ramie nano-cellulose fully soak swelling.
Polylactic resin (Nature Works company of the U.S., 2002D model) is put in 60 DEG C of baking ovens and dry
Dry 40h, makes moisture dry completely.Weighed polylactic resin is dissolved in acetone solvent, stirs at 40 DEG C
Mix 4h, make polylactic resin be completely dissolved.
2.00g hardwood xylan (for the 10% of ramie nano-cellulose consumption) is put in a container, adds
Distilled water heats 2h at 75 DEG C, makes hardwood xylan fully dissolve.The ramie Nanowire after soaking will be soaked
Dimension element join in hardwood xylan solution, put into supersonic frequency be 30kHz, ultrasonic power output be 200W
Ultrasonic wave in disperse, at 70 DEG C, stir 2h with the speed mechanical of 1000rpm, finally obtain uniform and stable
Modified ramie nano-cellulose suspension.With the centrifuge that rotating speed is 10000rpm, mixture is centrifuged 4 times
Making it be layered, leached by supernatant liquor, the nano-cellulose suspension after concentration is put in vacuum freeze drier,
Sample uses liquid nitrogen quick freeze drying and moulding 6h under-50 DEG C and 30Pa pressure condition, after hydrophobic modification
Nano-cellulose powder put into refrigerating chamber store.
Modified ramie nanofiber powder is mixed with the organic solvent dissolved with PLA, poly-breast in mixture
Acid mass fraction is 95%, and the mass fraction of ramie nano-cellulose is 5%, and mixture heats at 60 DEG C
90min, is sufficiently stirred for the speed of 1200rpm, shakes 40min in the ultrasonic wave that supersonic frequency is 30kHz
Prepare casting liquid.Above-mentioned 20ml blend casting liquid is slowly poured over area is 80cm2Polystyrene mould
On plate, putting in vent cabinet at room temperature slow evaporation 24h, make solvent volatilize, the vacuum placing into 60 DEG C is dried
In case be dried 24h to remove residual solvent, in template formation the smooth atresia of layer of surface, compact structure thin
Film, finally takes off film and seals preservation.
The modified ramie nano-cellulose prepared below by the experimental verification present invention and PLA laminated film, ramie
Fiber crops nano-cellulose and PLA laminated film, the physical and mechanical properties of pure polylactic acid film.Use spiral micrometer
(Stanley company of the U.S.) measures the thickness of film, and 5 the diverse location measurements choosing every film ask flat
Average.With hot strength and the extension at break of omnipotent mechanics tester (American I nstron company) testing film
Rate, makes long 70mm, the rectangle of wide 10mm by film, arranges spacing for 25mm, stretching of test machine
Speed is 10mm/min, and each sample carries out 5 tests and averages.The film of preparation is cut into 20mm
The square of × 20mm, pours the garden soil of 8cm height in beaker into and to add 15ml concentration is 10g/L
Nitrogenous fertilizer (urea) solution.Film dried in vacuum drying chamber and weighs, imbedding beaker soil, every
Within 7 days, sampling first drying is weighed, and represents that its soil buries palliating degradation degree with weight-loss ratio.Water vapor permeation rate tester (in
Blue streak company of state) test water vapour permeability (WVTR), banana measuring instrument (U.S. Modern
Controls company) test OTR oxygen transmission rate.The physical and mechanical properties contrast of three kinds of films is as shown in table 3.
Pure polylactic acid film and PLA laminated film physical and mechanical properties contrast test result in table 3 embodiment 3
As can be seen from Table 3, in three kinds of films, performance most preferably modified ramie nano-cellulose/PLA is multiple
Close film, next to that ramie nano-cellulose/PLA laminated film.The thickness difference of three kinds of films is little,
The addition of modified ramie nano-cellulose can be obviously enhanced the mechanical property of polylactic acid film, hot strength from
30.9MPa increases to 53.7MPa, and elongation at break increases to 28.2% from 6.1%, and laminated film toughness has bright
Aobvious raising.The addition of modified ramie nano-cellulose simultaneously also can significantly improve the degraded speed of PLA laminated film
Spending, the degradable time of PLA laminated film can be kept to 184 days from 295 days.The modified ramie of preparation is received
Rice cellulose and PLA laminated film good air permeability, water vapour permeability is from 214g/ (m224h) carry
High to 537g/ (m224h), OTR oxygen transmission rate is from 317cm3/(m2D) 473cm is brought up to3/(m2·d)。
Claims (10)
1. a modified ramie nano-cellulose and the preparation method of PLA laminated film, it is characterised in that: the party
Method is made up of following 3 steps:
Step 1: ramie nano-cellulose and PLA pretreatment
Ramie nano-cellulose is put into equilibrium water conten in the container with sealing ring, measures ramie nano-cellulose
Regain；Weigh ramie nano-cellulose quality, calculate ramie nano-cellulose dry weight according to regain；?
Ramie nano-cellulose adds distilled water, makes ramie nano-cellulose fully soak by distilled water immersion molten
Swollen；
Being put into by polylactic resin in baking oven and dry, the polylactic resin dried completely by moisture is dissolved in organic solvent
In, stir at a set temperature, make polylactic resin be completely dissolved；
Step 2: the hydrophobic modification of ramie nano-cellulose
Hardwood xylan is put in a container, add distilled water and heat, making hardwood xylan fully dissolve；
Ramie nano-cellulose after soaking wetting joins in this hardwood xylan solution, puts in ultrasonic wave and divides
Dissipate, and obtain uniform and stable modified ramie nano-cellulose suspension by mechanical agitation；By prepared mixing
Thing is centrifuged layering, is leached by supernatant liquor, and the ramie nano-cellulose suspension after remaining concentration is put into
In vacuum freeze drier, and liquid-nitrogen freeze drying is used to be molded, by the ramie nanofiber after hydrophobic modification
Element powder is put into refrigerating chamber and is stored；
Step 3: prepared by laminated film
Modified ramie nanofiber powder is mixed with the organic solvent dissolved with PLA, heating, fully stir
Mix and ultrasonic vibration, prepare casting liquid；This casting liquid is poured on polystyrene moulding, puts in vent cabinet
At room temperature solvent flashing, places in vacuum drying oven and is dried to remove residual solvent, forms one layer in template
Film, is modified ramie nano-cellulose and the PLA laminated film of required preparation, finally takes off film and seal guarantor
Deposit.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 1, the amount of the distilled water added in ramie nano-cellulose is: make
Ramie nano-cellulose solid mass percent concentration in distilled water is 0.5%～3%；During distilled water immersion
Between be 12～48h.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 1, the drying temperature of polylactic resin is 40～80 DEG C, drying time
It is 12～60h；The design temperature of stirring is 30～60 DEG C, and mixing time is 2～6h.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 1, the organic solvent dissolving polylactic resin is oxolane, chloroform,
Dichloromethane, acetone, benzene, toluene, formic acid, dioxane, one or more in tetrachloromethane.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 2, hardwood xylan solution temperature is 60～95 DEG C, and the heat time is
0.5～3h；Hardwood xylan consumption is the 5%～20% of ramie nano-cellulose consumption.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 2, the frequency of ultrasonic disperse is 20～40kHz, ultrasonic disperse defeated
Going out power is 100～300W；Carrying out mechanical agitation at a temperature of 50～90 DEG C, mechanical agitation speed is
800～1200rpm, the mechanical agitation time is 1～4h.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 2, mixture in container is centrifuged point by the method for centrifuge washing
Layer, centrifuge speed is 6000～12000rpm, and centrifugal number of times is 3～6 times；Employing liquid-nitrogen freeze drying is molded
Temperature be-40～-60 DEG C, pressure is 10～60Pa, and the time is 4～10h.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 3, by modified ramie nanofiber powder and dissolved with PLA
The mixed heating-up temperature of organic solvent is 50～90 DEG C, and the heat time is 30～120min, mechanical agitation speed
Being 1000～1400rpm, ultrasonic vibration frequency is 20～40kHz, and the ultrasonic vibration time is 30～60min.
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 3, in the casting liquid prepared, PLA mass fraction is 90%～99%,
The mass fraction of ramie nano-cellulose is 1%～10%；The amount of the casting liquid being poured on polystyrene moulding is
5～40ml, polystyrene moulding area is 40～120cm2。
A kind of modified ramie nano-cellulose the most as claimed in claim 1 and the preparation side of PLA laminated film
Method, it is characterised in that: in described step 3, the time in vent cabinet of putting into is 12～48h；In vacuum drying oven
Baking temperature is 40～80 DEG C, and drying time is 12～36h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410217621.5A CN103992493B (en) | 2014-05-20 | 2014-05-20 | A kind of modified ramie nano-cellulose and the preparation method of PLA laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410217621.5A CN103992493B (en) | 2014-05-20 | 2014-05-20 | A kind of modified ramie nano-cellulose and the preparation method of PLA laminated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103992493A CN103992493A (en) | 2014-08-20 |
| CN103992493B true CN103992493B (en) | 2016-08-31 |
Family
ID=51306851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410217621.5A Expired - Fee Related CN103992493B (en) | 2014-05-20 | 2014-05-20 | A kind of modified ramie nano-cellulose and the preparation method of PLA laminated film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103992493B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504708A (en) * | 2015-12-03 | 2016-04-20 | 丁玉琴 | Preparation method of ramie fiber/ basalt fiber/ polylactic acid ternary composite |
| CN111088602B (en) * | 2019-12-24 | 2022-02-15 | 福建恒安集团有限公司 | High-flexibility biodegradable non-woven fabric |
| TWI831008B (en) * | 2020-05-04 | 2024-02-01 | 大仁 陳 | Biodegradable material and biodegradable food material |
| CN111605261A (en) * | 2020-05-14 | 2020-09-01 | 江门市玛斯特包装有限公司 | Degradable bag capable of being vacuumized and preparation method thereof |
| CN113512280A (en) * | 2021-05-19 | 2021-10-19 | 青岛科技大学 | Preparation method of nanocellulose-based plastic film |
| CN114479139B (en) * | 2022-01-14 | 2023-08-25 | 江西冠德新材科技股份有限公司 | Fiber-based degradable film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6485530B1 (en) * | 1998-03-24 | 2002-11-26 | Nano-Tex, Llc | Modified textile and other materials and methods for their preparation |
| CN102211364A (en) * | 2011-05-17 | 2011-10-12 | 东华大学 | Method for improving adhesive property of ramie fibre-thermoplastic resin interface |
| WO2012120198A1 (en) * | 2011-03-07 | 2012-09-13 | Aalto University Foundation | Double click technology |
| CN103088626A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Method for improving ramie hydrophobicity through CF4 (carbon tetrafluoride) low-temperature plasma treatment |
| CN103614915A (en) * | 2013-10-24 | 2014-03-05 | 浙江理工大学 | Super-hydrophobic natural fiber fabric and preparation method thereof |
-
2014
- 2014-05-20 CN CN201410217621.5A patent/CN103992493B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6485530B1 (en) * | 1998-03-24 | 2002-11-26 | Nano-Tex, Llc | Modified textile and other materials and methods for their preparation |
| WO2012120198A1 (en) * | 2011-03-07 | 2012-09-13 | Aalto University Foundation | Double click technology |
| CN102211364A (en) * | 2011-05-17 | 2011-10-12 | 东华大学 | Method for improving adhesive property of ramie fibre-thermoplastic resin interface |
| CN103088626A (en) * | 2013-01-16 | 2013-05-08 | 天津工业大学 | Method for improving ramie hydrophobicity through CF4 (carbon tetrafluoride) low-temperature plasma treatment |
| CN103614915A (en) * | 2013-10-24 | 2014-03-05 | 浙江理工大学 | Super-hydrophobic natural fiber fabric and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Cellulose diacetate-graft-poly(lactic acid)s: synthesis of wide-ranging compositions and their thermal and mechanical properties";Yoshikuni Teramoto 等;《Polymer》;20031231;第44卷(第9期);第2701-2709页 * |
| "剑麻纤维增强聚丙烯复合材料的制备及性能研究";韩海山 等;《工程塑料应用》;20091231;第37卷(第5期);第21-25页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103992493A (en) | 2014-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103992493B (en) | A kind of modified ramie nano-cellulose and the preparation method of PLA laminated film | |
| Lalit et al. | Natural fibers and biopolymers characterization: A future potential composite material | |
| Sahari et al. | A new approach to use Arenga pinnata as sustainable biopolymer: Effects of plasticizers on physical properties | |
| Sreekumar et al. | Effect of fiber surface modification on the mechanical and water absorption characteristics of sisal/polyester composites fabricated by resin transfer molding | |
| Ye et al. | Bio-based composites fabricated from wood fibers through self-bonding technology | |
| Srithep et al. | Nanofibrillated cellulose (NFC) reinforced polyvinyl alcohol (PVOH) nanocomposites: properties, solubility of carbon dioxide, and foaming | |
| Raghavendra Rao et al. | Flexural and compressive properties of bamboo and glass fiber-reinforced epoxy hybrid composites | |
| CN105671937A (en) | Modification method of ramie fibers using as environment-friendly composite material reinforcement | |
| Zhang et al. | Starch-based rehealable and degradable bioplastic enabled by dynamic imine chemistry | |
| CN102304238B (en) | Renewable cellulose composite film and preparation method thereof | |
| Espinach Orús et al. | High stiffness performance alpha-grass pulp fiber reinforced thermoplastic starch-based fully biodegradable composites | |
| CN107641242B (en) | Injection molding material | |
| WO2017084227A1 (en) | A lightweight environmentally friendly biomass packaging material and preparation method therefor | |
| CN101770773B (en) | Sound insulation composite material of bamboo fibrofelt and polypropylene and preparing method thereof | |
| Zhang et al. | Fully biodegradable, hydrophobic, enhanced barrier starch bio-composites with sandwich structure by simulating wood | |
| Sharma et al. | Development and characterization of fibre reinforced material based on potato starch and jute fibre | |
| CN109438772B (en) | Edible packaging film and preparation method and application thereof | |
| Smoca | Water absorption properties of hemp fibres reinforced PLA bio-composites | |
| Nguyen et al. | Treatment of Water Hyacinth Fibers to Improve Mechanical and Microstructural Properties of Green Composite Materials | |
| CN107698784A (en) | A kind of preparation method of dialdehyde nano-cellulose and chitosan complex film | |
| CN108017878A (en) | A kind of modified nanometer cellulose plasticizing phenol formaldehyde and preparation method thereof | |
| CN104194015B (en) | A kind of preparation method of food packaging soybean protein and sodium alginate cross-linking film | |
| Ramesh et al. | Development and evaluation of water absorption, compression and impact properties of okra Nanofibrillated cellulose reinforcement in epoxy resin composites | |
| Chen | Study on mechanical and thermal performance of building energy-saving wall with insulation materials | |
| CN204982171U (en) | High strength degradable regeneration silk protein fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160831 Termination date: 20190520 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |