CN103992493A - Preparation method of modified ramie nano-cellulose and polylactic acid composite film - Google Patents
Preparation method of modified ramie nano-cellulose and polylactic acid composite film Download PDFInfo
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Abstract
The invention provides a preparation method of a modified ramie nano-cellulose and polylactic acid composite film. Two biomass resources of ramie nano-cellulose and polylactic acid resin are taken as raw materials, hardwood xylan is utilized to perform hydrophobic modification on ramie nano-cellulose, polylactic acid and ramie nano-cellulose after modification are dissolved in an organic solvent and a blend casting solution is slowly poured onto a polystyrene template by adopting a solvent casting method, placed into a fume hood to naturally volatilize the solvent at room temperature and finally cured and formed to prepare the modified ramie nano-cellulose and polylactic acid composite film. The method provided by the invention is simple to operate and low in production cost; the used materials are degradable biomass materials, low in price and easy to obtain; the prepared film has very high tensile strength and elongation at break, simultaneously has the advantages of good air permeability, biodegradability, stable quality, good softness and biocompatibility and can be used in the fields of food packaging materials, agricultural films, packaging films for industrial products and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of modified ramie nano-cellulose and poly(lactic acid) laminated film, belong to preparation and the nano composite material technical field of degradable biological matter thin-film material.
Background technology
Along with the progress of technology and the enhancing of environmental protection ideas, the Application and Development of the biomass Green Composites of natural plant fibre and the compound preparation of bio-degradable plastics receives people's concern day by day, and becomes gradually inexorable trend and the study hotspot of matrix material development.Poly(lactic acid) (PLA) is to take the polymkeric substance that lactic acid obtains as main raw material polymerization, raw material sources fully and can regenerate, degraded product is carbonic acid gas and water, to air and soil, can not produce toxic action, be a kind of multiduty ecological, environmental protective macromolecular material, there is good thermomechanical property and optical property, there is good tensile strength and extensibility simultaneously, can adopt various ways to process according to different demands, make various types of products.The polylactic acid film making through forming methods such as blowing, calendering, solvent evaporates, there is good biocompatibility and good ventilation property and antibacterial anti-mildew characteristic, in food packaging film, agricultural, by aspects such as films, can replace the use of difficult degradation " white pollution " plastics films such as polypropylene, polyvinyl chloride, have broad application prospects.
But, due to the structural weakness of poly(lactic acid) itself, cause that its polylactic acid film intensity is low, fragility is high, poor toughness, in order to improve the mechanical property of polylactic acid film, increase its molecule chain flexibility and toughness, can adopt the abundant vegetable fibre of nature as the reinforcement of lactic acid composite material.The nano-cellulose extracting from ramee, has high specific surface area, high degree of crystallinity, low thermal expansivity and good mechanical property, and intensity and hardness that can reinforced composite, improve its physical and mechanical property.Yet, because natural plant fibre has stronger polarity and wetting ability, make the interface adhesion between itself and non-polar resin poor, can cause the function of its wild phase significantly to decline.Therefore nano-cellulose, before introducing, carry out hydrophobic modification to it, reduces wetting ability and polarity, the interface compatibility between raising and hydrophobic resin matrix.Hardwood xylan is a kind of in xylan, belongs to the hemicellulose components in vegetable cell, is the very abundant polysaccharide of nature content.Hardwood xylan exists with the form of O-ethanoyl-4-O-methyl-glucuronic acid-xylan; this type of xylan is how highly acetylated in C-3 site; a large amount of ethanoyl and hydroxyl are present in surface; very easily with nano-cellulose in Sauerstoffatom play bonding action; be connected with cellulosic hydrogen bond, form stable tridimensional network simultaneously.In hardwood xylan, contain ethanoyl, ethanoyl has hydrophobicity, by bridge joint effect, makes whole cellulose macromolecule chain have hydrophobic performance, and the physical strength of nano-cellulose, flexility and hydrophobic performance have greatly improved thus.
The several different methods such as composite material film preparation technology has injection moulding, extrudes, hot pressing, dipping, pressure layer, blend kneading and solvent casting.Solvent casting wherein (solvent casting), refers to and selects suitable solvent that polymer dissolution is made to casting liquid, will cast drop on substrate or watch-glass, allows under solvent room temperature condition and naturally volatilizees, final curing film forming in stink cupboard.Solvent casting method masking technique is simple to operate efficient, and filming condition is gentle, can control according to concentration, consumption and the substrate area of casting liquid the thickness of film forming.Between the film simultaneously making, connect closely, film finished product internal stress is little, has good physical strength and mechanical property, and tool has been widely used.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of to take ramie nano-cellulose and two kinds of biomass resources of polylactic resin be raw material, makes the method for the composite material film with good snappiness and biocompatibility.
In order to solve the problems of the technologies described above, technical scheme of the present invention is to provide the preparation method of a kind of modified ramie nano-cellulose and poly(lactic acid) laminated film, it is characterized in that: the method is comprised of following 3 steps:
Step 1: ramie nano-cellulose and poly(lactic acid) pre-treatment
Ramie nano-cellulose is put into the container equilibrium water content with sealing-ring, measure the moisture regain of ramie nano-cellulose; Weigh ramie nano-cellulose quality, according to moisture regain, calculate ramie nano-cellulose dry weight; In ramie nano-cellulose, add distilled water, by distilled water immersion, make the fully wetting swelling of ramie nano-cellulose;
Polylactic resin is put into baking oven and dry, the polylactic resin that moisture is dried is completely dissolved in organic solvent, under design temperature, stirs, and polylactic resin is dissolved completely;
Step 2: the hydrophobic modification of ramie nano-cellulose
Hardwood xylan is put into a container, add distilled water heating, hardwood xylan is fully dissolved; The ramie nano-cellulose soaking after soaking is joined in this hardwood xylan solution, put into ultrasonic wave and disperse, and obtain uniform and stable modified ramie nano-cellulose suspension by mechanical stirring; The mixture making is carried out to centrifugal layering, supernatant liquid is leached, ramie nano-cellulose suspension after remaining concentrating is put into vacuum freeze drier, and adopts liquid-nitrogen freeze drying moulding, the ramie nano-cellulose powder after hydrophobic modification is put into refrigeration chamber and store;
Step 3: laminated film preparation
Ramie nanofiber powder after modification is mixed with the organic solvent that is dissolved with poly(lactic acid), and heating, fully stirs and ultrasonic concussion, makes casting liquid; This casting liquid is poured on polystyrene moulding, put at room temperature solvent flashing of Fume Hoods, put into again vacuum drying oven dry to remove residual solvent, in template, form thin film, be modified ramie nano-cellulose and the poly(lactic acid) laminated film of required preparation, finally take off film phonograph seal and preserve.
Preferably, in described step 1, the amount of the distilled water adding in ramie nano-cellulose is: making the mass percent concentration of ramie nano-cellulose solid in distilled water is 0.5%～3%; The distilled water immersion time is 12～48h.
Preferably, in described step 1, the bake out temperature of polylactic resin is 40～80 ℃, and drying time is 12～60h; The design temperature stirring is 30～60 ℃, and churning time is 2～6h.
Preferably, in described step 1, the organic solvent that dissolves polylactic resin is tetrahydrofuran (THF), chloroform, methylene dichloride, acetone, benzene, toluene, formic acid ， diox, one or more in tetrachloromethane.
Preferably, in described step 2, hardwood xylan solvent temperature is 60～95 ℃, and be 0.5～3h heat-up time; Hardwood xylan consumption is 5%～20% of ramie nano-cellulose consumption.
Preferably, in described step 2, the frequency of ultrasonic dispersion is 20～40kHz, and the output rating of ultrasonic dispersion is 100～300W; At the temperature of 50～90 ℃, carry out mechanical stirring, mechanical stirring speed is 800～1200rpm, and the mechanical stirring time is 1～4h.
Preferably, in described step 2, by the method for centrifuge washing, mixture in container is carried out to centrifugal layering, centrifuge speed is 6000～12000rpm, and centrifugal number of times is 3～6 times; Adopting the temperature of liquid-nitrogen freeze drying moulding is-40～-60 ℃, and pressure is 10～60Pa, and the time is 4～10h.
Preferably, in described step 3, by the ramie nanofiber powder after modification, it is 50～90 ℃ with the mixed Heating temperature of organic solvent that is dissolved with poly(lactic acid), be 30～120min heat-up time, mechanical stirring speed is 1000～1400rpm, ultrasonic concussion frequency is 20～40kHz, and the ultrasonic concussion time is 30～60min.
Preferably, in described step 3, in the casting liquid making, poly(lactic acid) massfraction is 90%～99%, and the massfraction of ramie nano-cellulose is 1%～10%; The amount that is poured on the casting liquid on polystyrene moulding is 5～40ml, and polystyrene moulding area is 40～120cm
2.
Preferably, in described step 3, putting into the Fume Hoods time is 12～48h; In vacuum drying oven, drying temperature is 40～80 ℃, and be 12～36h time of drying.
Method provided by the invention has overcome the deficiencies in the prior art, simple to operate, production cost is low, can be respectively by the cast concentration of liquid and the evaporation area of template of control, control film thickness and evaporation rate of solvent, material therefor and modifier source are extensive, environmental protection, the film making is eco-friendly, biodegradable, while steady quality, there is good snappiness and biocompatibility, after film vacuum can being dried, for packaging material for food, agricultural, use the fields such as film and mechanicals packing film.
Embodiment
For the present invention is become apparent, hereby, with several preferred embodiments, be described in detail below.
Embodiment 1
The preparation method of a kind of modified ramie nano-cellulose and poly(lactic acid) laminated film is as follows:
Ramie nano-cellulose is put into the container equilibrium water content with sealing-ring, and the moisture regain of measuring ramie nano-cellulose is 8.7%.Weigh ramie nano-cellulose quality 22.10g, according to moisture regain, calculating its dry weight is 20.18g.Add a certain amount of distilled water, making ramie nano-cellulose mass percent concentration is 3%, soaks 24h, makes the fully wetting swelling of ramie nano-cellulose.
Polylactic resin (U.S. Nature Works company, 2002D model) is put into 40 ℃ of baking ovens and dry 12h, moisture is dried completely.The polylactic resin weighing is dissolved in chloroform solvent, at 30 ℃, stirs 2h, polylactic resin is dissolved completely.
By 1.01g hardwood xylan (for ramie nano-cellulose consumption 5%) put into a container, add distilled water at 60 ℃, to heat 0.5h, hardwood xylan is fully dissolved.The ramie nano-cellulose soaking after soaking is joined in hardwood xylan solution, putting into ultrasonic frequency is that the ultrasonic wave that 20kHz, ultrasonic output rating are 100W is disperseed, speed mechanical with 800rpm at 50 ℃ stirs 1h, finally obtains uniform and stable modified ramie nano-cellulose suspension.The whizzer that is 6000rpm with rotating speed makes its layering centrifugal 3 times by mixture, supernatant liquid is leached, nano-cellulose suspension after concentrated is put into vacuum freeze drier, sample adopts the rapid lyophilize moulding of liquid nitrogen 4h under-40 ℃ and 10Pa pressure condition, the nano-cellulose powder after hydrophobic modification is put into refrigeration chamber and store.
Ramie nanofiber powder after modification is mixed with the organic solvent that is dissolved with poly(lactic acid), in mixture, poly(lactic acid) massfraction is 90%, the massfraction of ramie nano-cellulose is 10%, mixture heats 30min at 50 ℃, speed with 1000rpm fully stirs, and shakes 30min make casting liquid in ultrasonic frequency in the ultrasonic wave that is 20kHz.It is 40cm that above-mentioned 5ml blend casting liquid is slowly poured over to area
2polystyrene moulding on, put at room temperature slow evaporation 12h of Fume Hoods, make solvent evaporates, then put into the dry 12h of vacuum drying oven of 40 ℃ to remove residual solvent, in template, form the film of the smooth atresia of layer of surface, compact structure, finally take off film phonograph seal and preserve.
The physical and mechanical properties of the modified ramie nano-cellulose of preparing below by experimental verification the present invention and poly(lactic acid) laminated film, ramie nano-cellulose and poly(lactic acid) laminated film, pure polylactic acid film.With spiral micrometer (U.S. Stanley company), measure the thickness of film, choose 5 different positions measurements of every film and average.Tensile strength and elongation at break with omnipotent mechanics tester (American I nstron company) testing film, film is made to the rectangle of long 70mm, wide 10mm, spacing for 25mm of test machine is set, and draw speed is 10mm/min, and each sample carries out 5 tests and averages.The film of preparation is cut into the square of 20mm * 20mm, in beaker, pouring the garden soil of 8cm height into and adding 15ml concentration is nitrogenous fertilizer (urea) solution of 10g/L.Film dried in vacuum drying oven and weigh, imbedding beaker soil, every 7 days sampling first dryings, weighing, with rate of weight loss, representing that its soil buries palliating degradation degree.Water vapor permeation rate tester (Chinese blue streak company) test water vapour permeability (WVTR), banana survey meter (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 poly(lactic acid) laminated film physical and mechanical properties contrast test result in table 1 embodiment 1
As can be seen from Table 1, what three kinds of film performances were best is modified ramie nano-cellulose/poly(lactic acid) laminated film, is secondly ramie nano-cellulose/poly(lactic acid) laminated film.The thickness difference of three kinds of films is little, modified ramie nano-cellulose add the mechanical property that can significantly strengthen polylactic acid film, tensile strength is increased to 52.6MPa from 29.8MPa, and elongation at break is increased to 27.4% from 5.9%, and laminated film toughness is significantly improved.Simultaneously modified ramie nano-cellulose add the degradation speed that also can significantly improve poly(lactic acid) laminated film, the degradable time of poly(lactic acid) laminated film can be kept to 181 days from 293 days.Modified ramie nano-cellulose and the poly(lactic acid) laminated film good air permeability of preparation, water vapour permeability is from 217g/m
2/ 24h brings up to 523g/m
2/ 24h, OTR oxygen transmission rate is from 320cm
3/ m
2d brings up to 476cm
3/ m
2d.
Embodiment 2
The preparation method of a kind of modified ramie nano-cellulose and poly(lactic acid) laminated film is as follows:
Ramie nano-cellulose is put into the container equilibrium water content with sealing-ring, and the moisture regain of measuring ramie nano-cellulose is 8.8%.Weigh ramie nano-cellulose quality 21.40g, according to moisture regain, calculating its dry weight is 19.52g.Add a certain amount of distilled water, making ramie nano-cellulose mass percent concentration is 0.5%, soaks 48h, makes the fully wetting swelling of ramie nano-cellulose.
Polylactic resin (U.S. Nature Works company, 2002D model) is put into 80 ℃ of baking ovens and dry 60h, moisture is dried completely.The polylactic resin weighing is dissolved in tetrahydrofuran solvent, at 60 ℃, stirs 6h, polylactic resin is dissolved completely.
By 4.28g hardwood xylan (for ramie nano-cellulose consumption 20%) put into a container, add distilled water at 95 ℃, to heat 3h, hardwood xylan is fully dissolved.The ramie nano-cellulose soaking after soaking is joined in hardwood xylan solution, putting into ultrasonic frequency is that the ultrasonic wave that 40kHz, ultrasonic output rating are 300W is disperseed, speed mechanical with 1200rpm at 90 ℃ stirs 4h, finally obtains uniform and stable modified ramie nano-cellulose suspension.The whizzer that is 12000rpm with rotating speed makes its layering centrifugal 6 times by mixture, supernatant liquid is leached, nano-cellulose suspension after concentrated is put into vacuum freeze drier, sample adopts the rapid lyophilize moulding of liquid nitrogen 10h under-60 ℃ and 60Pa pressure condition, the nano-cellulose powder after hydrophobic modification is put into refrigeration chamber and store.
Ramie nanofiber powder after modification is mixed with the organic solvent that is dissolved with poly(lactic acid), in mixture, poly(lactic acid) massfraction is 99%, the massfraction of ramie nano-cellulose is 1%, mixture heats 120min at 90 ℃, speed with 1400rpm fully stirs, and shakes 60min make casting liquid in ultrasonic frequency in the ultrasonic wave that is 40kHz.It is 120cm that above-mentioned 40ml blend casting liquid is slowly poured over to area
2polystyrene moulding on, put at room temperature slow evaporation 48h of Fume Hoods, make solvent evaporates, then put into the dry 36h of vacuum drying oven of 80 ℃ to remove residual solvent, in template, form the film of the smooth atresia of layer of surface, compact structure, finally take off film phonograph seal and preserve.
The physical and mechanical properties of the modified ramie nano-cellulose of preparing below by experimental verification the present invention and poly(lactic acid) laminated film, ramie nano-cellulose and poly(lactic acid) laminated film, pure polylactic acid film.With spiral micrometer (U.S. Stanley company), measure the thickness of film, choose 5 different positions measurements of every film and average.Tensile strength and elongation at break with omnipotent mechanics tester (American I nstron company) testing film, film is made to the rectangle of long 70mm, wide 10mm, spacing for 25mm of test machine is set, and draw speed is 10mm/min, and each sample carries out 5 tests and averages.The film of preparation is cut into the square of 20mm * 20mm, in beaker, pouring the garden soil of 8cm height into and adding 15ml concentration is nitrogenous fertilizer (urea) solution of 10g/L.Film dried in vacuum drying oven and weigh, imbedding beaker soil, every 7 days sampling first dryings, weighing, with rate of weight loss, representing that its soil buries palliating degradation degree.Water vapor permeation rate tester (Chinese blue streak company) test water vapour permeability (WVTR), banana survey meter (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 poly(lactic acid) laminated film physical and mechanical properties contrast test result in table 2 embodiment 2
As can be seen from Table 2, what three kinds of film performances were best is modified ramie nano-cellulose/poly(lactic acid) laminated film, is secondly ramie nano-cellulose/poly(lactic acid) laminated film.The thickness difference of three kinds of films is little, modified ramie nano-cellulose add the mechanical property that can significantly strengthen polylactic acid film, tensile strength is increased to 53.5MPa from 28.0MPa, and elongation at break is increased to 28.0% from 6.1%, and laminated film toughness is significantly improved.Simultaneously modified ramie nano-cellulose add the degradation speed that also can significantly improve poly(lactic acid) laminated film, the degradable time of poly(lactic acid) laminated film can be kept to 184 days from 296 days.Modified ramie nano-cellulose and the poly(lactic acid) laminated film good air permeability of preparation, water vapour permeability is from 202g/m
2/ 24h brings up to 524g/m
2/ 24h, OTR oxygen transmission rate is from 330cm
3/ m
2d brings up to 482cm
3/ m
2d.
Embodiment 3
The preparation method of a kind of modified ramie nano-cellulose and poly(lactic acid) laminated film is as follows:
Ramie nano-cellulose is put into the container equilibrium water content with sealing-ring, and the moisture regain of measuring ramie nano-cellulose is 9.0%.Weigh ramie nano-cellulose quality 22.00g, according to moisture regain, calculating its dry weight is 20.02g.Add a certain amount of distilled water, making ramie nano-cellulose mass percent concentration is 1.5%, soaks 12h, makes the fully wetting swelling of ramie nano-cellulose.
Polylactic resin (U.S. Nature Works company, 2002D model) is put into 60 ℃ of baking ovens and dry 40h, moisture is dried completely.The polylactic resin weighing is dissolved in acetone solvent, at 40 ℃, stirs 4h, polylactic resin is dissolved completely.
By 2.00g hardwood xylan (for ramie nano-cellulose consumption 10%) put into a container, add distilled water at 75 ℃, to heat 2h, hardwood xylan is fully dissolved.The ramie nano-cellulose soaking after soaking is joined in hardwood xylan solution, putting into ultrasonic frequency is that the ultrasonic wave that 30kHz, ultrasonic output rating are 200W is disperseed, speed mechanical with 1000rpm at 70 ℃ stirs 2h, finally obtains uniform and stable modified ramie nano-cellulose suspension.The whizzer that is 10000rpm with rotating speed makes its layering centrifugal 4 times by mixture, supernatant liquid is leached, nano-cellulose suspension after concentrated is put into vacuum freeze drier, sample adopts the rapid lyophilize moulding of liquid nitrogen 6h under-50 ℃ and 30Pa pressure condition, the nano-cellulose powder after hydrophobic modification is put into refrigeration chamber and store.
Ramie nanofiber powder after modification is mixed with the organic solvent that is dissolved with poly(lactic acid), in mixture, poly(lactic acid) massfraction is 95%, the massfraction of ramie nano-cellulose is 5%, mixture heats 90min at 60 ℃, speed with 1200rpm fully stirs, and shakes 40min make casting liquid in ultrasonic frequency in the ultrasonic wave that is 30kHz.It is 80cm that above-mentioned 20ml blend casting liquid is slowly poured over to area
2polystyrene moulding on, put at room temperature slow evaporation 24h of Fume Hoods, make solvent evaporates, then put into the dry 24h of vacuum drying oven of 60 ℃ to remove residual solvent, in template, form the film of the smooth atresia of layer of surface, compact structure, finally take off film phonograph seal and preserve.
The physical and mechanical properties of the modified ramie nano-cellulose of preparing below by experimental verification the present invention and poly(lactic acid) laminated film, ramie nano-cellulose and poly(lactic acid) laminated film, pure polylactic acid film.With spiral micrometer (U.S. Stanley company), measure the thickness of film, choose 5 different positions measurements of every film and average.Tensile strength and elongation at break with omnipotent mechanics tester (American I nstron company) testing film, film is made to the rectangle of long 70mm, wide 10mm, spacing for 25mm of test machine is set, and draw speed is 10mm/min, and each sample carries out 5 tests and averages.The film of preparation is cut into the square of 20mm * 20mm, in beaker, pouring the garden soil of 8cm height into and adding 15ml concentration is nitrogenous fertilizer (urea) solution of 10g/L.Film dried in vacuum drying oven and weigh, imbedding beaker soil, every 7 days sampling first dryings, weighing, with rate of weight loss, representing that its soil buries palliating degradation degree.Water vapor permeation rate tester (Chinese blue streak company) test water vapour permeability (WVTR), banana survey meter (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 poly(lactic acid) laminated film physical and mechanical properties contrast test result in table 3 embodiment 3
As can be seen from Table 3, what three kinds of film performances were best is modified ramie nano-cellulose/poly(lactic acid) laminated film, is secondly ramie nano-cellulose/poly(lactic acid) laminated film.The thickness difference of three kinds of films is little, modified ramie nano-cellulose add the mechanical property that can significantly strengthen polylactic acid film, tensile strength is increased to 53.7MPa from 30.9MPa, and elongation at break is increased to 28.2% from 6.1%, and laminated film toughness is significantly improved.Simultaneously modified ramie nano-cellulose add the degradation speed that also can significantly improve poly(lactic acid) laminated film, the degradable time of poly(lactic acid) laminated film can be kept to 184 days from 295 days.Modified ramie nano-cellulose and the poly(lactic acid) laminated film good air permeability of preparation, water vapour permeability is from 214g/m
2/ 24h brings up to 537g/m
2/ 24h, OTR oxygen transmission rate is from 317cm
3/ m
2d brings up to 473cm
3/ m
2d.
Claims (10)
1. a preparation method for modified ramie nano-cellulose and poly(lactic acid) laminated film, is characterized in that: the method is comprised of following 3 steps:
Step 1: ramie nano-cellulose and poly(lactic acid) pre-treatment
Ramie nano-cellulose is put into the container equilibrium water content with sealing-ring, measure the moisture regain of ramie nano-cellulose; Weigh ramie nano-cellulose quality, according to moisture regain, calculate ramie nano-cellulose dry weight; In ramie nano-cellulose, add distilled water, by distilled water immersion, make the fully wetting swelling of ramie nano-cellulose;
Polylactic resin is put into baking oven and dry, the polylactic resin that moisture is dried is completely dissolved in organic solvent, under design temperature, stirs, and polylactic resin is dissolved completely;
Step 2: the hydrophobic modification of ramie nano-cellulose
Hardwood xylan is put into a container, add distilled water heating, hardwood xylan is fully dissolved; The ramie nano-cellulose soaking after soaking is joined in this hardwood xylan solution, put into ultrasonic wave and disperse, and obtain uniform and stable modified ramie nano-cellulose suspension by mechanical stirring; The mixture making is carried out to centrifugal layering, supernatant liquid is leached, ramie nano-cellulose suspension after remaining concentrating is put into vacuum freeze drier, and adopts liquid-nitrogen freeze drying moulding, the ramie nano-cellulose powder after hydrophobic modification is put into refrigeration chamber and store;
Step 3: laminated film preparation
Ramie nanofiber powder after modification is mixed with the organic solvent that is dissolved with poly(lactic acid), and heating, fully stirs and ultrasonic concussion, makes casting liquid; This casting liquid is poured on polystyrene moulding, put at room temperature solvent flashing of Fume Hoods, put into again vacuum drying oven dry to remove residual solvent, in template, form thin film, be modified ramie nano-cellulose and the poly(lactic acid) laminated film of required preparation, finally take off film phonograph seal and preserve.
2. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, it is characterized in that: in described step 1, the amount of the distilled water adding in ramie nano-cellulose is: making the mass percent concentration of ramie nano-cellulose solid in distilled water is 0.5%～3%; The distilled water immersion time is 12～48h.
3. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, is characterized in that: in described step 1, the bake out temperature of polylactic resin is 40～80 ℃, and drying time is 12～60h; The design temperature stirring is 30～60 ℃, and churning time is 2～6h.
4. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, it is characterized in that: in described step 1, the organic solvent that dissolves polylactic resin is tetrahydrofuran (THF), chloroform, methylene dichloride, acetone, benzene, toluene, formic acid diox, one or more in tetrachloromethane.
5. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, is characterized in that: in described step 2, hardwood xylan solvent temperature is 60～95 ℃, and be 0.5～3h heat-up time; Hardwood xylan consumption is 5%～20% of ramie nano-cellulose consumption.
6. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, is characterized in that: in described step 2, the frequency of ultrasonic dispersion is 20～40kHz, and the output rating of ultrasonic dispersion is 100～300W; At the temperature of 50～90 ℃, carry out mechanical stirring, mechanical stirring speed is 800～1200rpm, and the mechanical stirring time is 1～4h.
7. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, it is characterized in that: in described step 2, by the method for centrifuge washing, mixture in container is carried out to centrifugal layering, centrifuge speed is 6000～12000rpm, and centrifugal number of times is 3～6 times; Adopting the temperature of liquid-nitrogen freeze drying moulding is-40～-60 ℃, and pressure is 10～60Pa, and the time is 4～10h.
8. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, it is characterized in that: in described step 3, by the ramie nanofiber powder after modification, it is 50～90 ℃ with the mixed Heating temperature of organic solvent that is dissolved with poly(lactic acid), be 30～120min heat-up time, mechanical stirring speed is 1000～1400rpm, ultrasonic concussion frequency is 20～40kHz, and the ultrasonic concussion time is 30～60min.
9. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, it is characterized in that: in described step 3, in the casting liquid making, poly(lactic acid) massfraction is 90%～99%, and the massfraction of ramie nano-cellulose is 1%～10%; The amount that is poured on the casting liquid on polystyrene moulding is 5～40ml, and polystyrene moulding area is 40～120cm
2.
10. the preparation method of a kind of modified ramie nano-cellulose as claimed in claim 1 and poly(lactic acid) laminated film, is characterized in that: in described step 3, putting into the Fume Hoods time is 12～48h; In vacuum drying oven, drying temperature is 40～80 ℃, and be 12～36h time of drying.
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| CN103992493B CN103992493B (en) | 2016-08-31 |
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| CN114479139A (en) * | 2022-01-14 | 2022-05-13 | 江西冠德新材科技股份有限公司 | Fiber-based degradable film and preparation method thereof |
| 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 |
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