CN108892793A - A kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film - Google Patents
A kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film Download PDFInfo
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Abstract
The present invention relates to packaging material fields, disclose a kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film, including：1）The preparation of nano-cellulose aqueous dispersions；2）The preparation of nanoclay suspension；3）Nano-cellulose/PVA/ nanoclay complex liquid preparation；4）To nano-cellulose/PVA/ nanoclay complex liquid standing and defoaming processing, levelling in mold is poured into, is dried in vacuo, nano-cellulose/PVA/ nanoclay composite membrane is made；5）Composite membrane is placed in impregnation in acyl chlorides/petroleum ether mixed liquor, then heating reaction, completes the chloride hydrophobic treatment of composite membrane.Composite film material prepared by the present invention not only has excellent oxygen and vapor water barriers performance, mechanical property and good biodegradability, and light transmittance is up to 89%, it is made to have extensive commercial applications potential in fields such as food fresh keeping packaging, Key works Drug packing, degradable green packaging materials.
Description
Technical field
The present invention relates to packaging material field more particularly to a kind of degradable green high-barrier high grade of transparency nano-celluloses
The preparation method of composite membrane.
Background technique
Since 21 century, a large amount of nondegradable package wastes have been produced by the plastic package material of raw material of oil product
Object has caused global environmental problem.In recent years, in order to adapt to every field to the new demand of packaging material, packaging material
Develop towards the directions such as high quality, high intensity, multi-functional, new process, lightweight.The development of world economy, environmental resource it is short
It lacks and the transformation of philosophy of life is so that people's environmental consciousness is increasingly enhanced, the concept of degradable green environment-friendly materials is come into being.
The green separated packaging material studied at present is divided into following four major class according to the type of raw material：(1) natural biological
Degradation material has many advantages, such as abundance, cheap, such as cellulose, starch, lignin, chitosan；(2) chemistry closes
At degradation material, such as polylactic acid (PLA), polyvinyl alcohol (PVA, PVOH), polycarbonate, polyurethane etc.；(3) Microbe synthesis
Degradation material, such as poly butyric ester (PHB)；(4) two or more natural or synthetic degradable material blending or total
Mixed type degradable high polymer material made of poly-, such as " Novon " starch mixing material of Warner-Lambert company of the U.S..
But these green separated packaging materials generally all exist that mechanical property is not ideal enough, barrier property is left to be desired, transparency not
The problems such as sufficient.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of degradable green high-barrier high grade of transparency nanofibers
The preparation method of plain composite membrane, the present invention prepare composite membrane by the way that nano-cellulose and nanoclay are added in PVA, it is therefore an objective to
The oxygen barrier property and strength character of composite membrane are promoted using the synergistic effect of the two, while being handled using subsequent chloride
The vapor water barriers performance for improving composite membrane, substitutes existing petroleum base polymeric plastics film.The method of the present invention is low in cost, system
Composite membrane degradable green, the obstructing capacity obtained is high, light transmittance is high, excellent in mechanical performance.
The specific technical solution of the present invention is：A kind of degradable green high-barrier high grade of transparency nano cellulose composite film
Preparation method includes the following steps：
1) nano-cellulose gel is added to the water dilution, decentralized processing obtains nano-cellulose aqueous dispersions.
2) nanoclay inorganic particulate is added to the water, decentralized processing obtains nanoclay suspension.
3) PVA solution is prepared, nano-cellulose dispersion liquid is then added, nanoclay is then added in heating stirring mixing
Suspension continues to be stirred, and obtains nano-cellulose/PVA/ nanoclay complex liquid.
4) to nano-cellulose/PVA/ nanoclay complex liquid standing and defoaming processing, levelling in mold is poured into, vacuum is dry
It is dry, nano-cellulose/PVA/ nanoclay composite membrane is made.
5) composite membrane is placed in impregnation in acyl chlorides/petroleum ether mixed liquor, then heating reaction, completes the acyl of composite membrane
Chlorinated hydrophobic processing.
Both the present invention prepares composite membrane by the way that nano-cellulose and nanoclay are added in PVA, it is therefore an objective to using
Synergistic effect promotes the oxygen barrier property and strength character of composite membrane, while improving composite membrane using subsequent chloride processing
Vapor water barriers performance, substitute existing petroleum base polymeric plastics film.The method of the present invention is low in cost, composite membrane obtained
Degradable green, obstructing capacity are high, light transmittance is high, excellent in mechanical performance.
Specifically,
Nano-cellulose is to pass through mechanical, chemistry, enzymatic treatment by plant cellulose and combine processing or generated by bacterium,
Having for obtaining is one-dimensional having a size of nanoscale cellulose.Nano-cellulose is broadly divided into following three categories：Fibrillated fibers of receiving are plain
(Nano-fibrillated Cellulose, that is, NFC, also known as cellulose nanometer fibril-Cellulose Nano-Fibrils are
CNF), nano micro crystal cellulose (Nano-Crystalline Cellulose, that is, NCC, also known as Cellulose nanocrystal-
Cellulose Nano-Crystals, that is, CNC), Nano bacteria cellulose (Bacterial Nano-Cellulose, i.e. BNC,
Abbreviation bacteria cellulose-Bacterial Cellulose, that is, BC), details are shown in Table 1.Above-mentioned nano-cellulose all have compared with
High crystallinity and cohesion energy density can be used as efficient oxygen obstruction substance and be subject to use raising oxygen barrier property
The reason of can be attributed to the uniform nanofibrils of nano-cellulose and can form the network structure of intensive complexity, nanofiber element coating
Lamination barrier can provide oxygen obstruction effect.It can also be had the advantage that using nano-cellulose biggish based on itself
Specific surface area and binding ability can be such that the mechanical property of composite material is significantly improved.
The preparation method and property of the different nano-celluloses of table 1
PVA can be combined with the hydroxyl on nano-cellulose, form intensive complicated network structure, effectively promotion composite membrane
Strength character.
The addition of nanoclay can further promote the barrier property of composite film material, its OTR oxygen transmission rate is made quantity occur
The decline of grade.
Subsequent chloride processing can be effectively improved the vapor water barriers performance of composite film material.
Preferably, step 1) is specially：Taking concentration is that the nano-cellulose gel of 0.5-1.5wt% is added to the water,
Be configured to concentration be 0.1~0.8wt% nano-cellulose solution, at 10000~15000r/min decentralized processing 5~
15min。
Preferably, step 2) is specially：Take nanoclay inorganic particulate to be added to the water, be formulated as concentration 0.5~
The nanoclay suspension of 5wt%, 2~6h of decentralized processing at 10000~15000r/min.
Preferably, step 3) is specially：It takes solid PVA soluble in water, is formulated as the PVA solution of concentration 5-10wt%,
Then nano-cellulose dispersion liquid is added, heating stirring mixes 1~3h in 90~100 DEG C of water-baths, and nanoclay is then added
Suspension continues to be stirred 2~4h, obtains nano-cellulose/PVA/ nanoclay complex liquid, wherein PVA, nanofiber
Plain, nanoclay quality accounting is 70~98: 1~15: 1~15.
Preferably, step 4) is specially：At nano-cellulose/PVA/ nanoclay complex liquid at room temperature standing and defoaming
4~8h is managed, levelling in polystyrene plastics mold is poured into, is dried in vacuo, obtains the composite membrane with a thickness of 50-100 μm；Wherein,
40~60 DEG C of drying temperature, vacuum degree -0.1MPa, 3~5d of time.
Preferably, step 5) is specially：Laminated film is placed in acyl chlorides/petroleum ether mixed liquor of 1~3wt% and is impregnated
2~4min is handled, 2~6min of reaction at 100-110 DEG C is then put in.
Preferably, the nano-cellulose be receive fibrillated fibers element, nano micro crystal cellulose, in Nano bacteria cellulose
At least one dimension is having a size of nanoscale cellulose；The nanoclay is bentonite, kaolin or vermiculite.
Preferably, the degree of polymerization of the PVA is between 600~2500, alcoholysis degree is between 80%~98%.
Preferably, the acyl chlorides is fat acyl chloride or caproyl chloride.
Preferably, the nano-cellulose passes through modification in step 1)：Nano-cellulose is added to its 8-12
Times quality, containing lactic acid bacteria, photosynthetic bacteria and saccharomycete and total bacteria concentration is heating in the mixed bacteria liquid of 0.01-0.02wt%
To 30-40 DEG C, ferment 1-2 days；Then nano-cellulose is made into aqueous solution, the NaOH that 3-5mol/L is added dropwise while stirring is molten
Liquid adjusts pH to neutrality；It is subsequently placed in 25-35 DEG C of water-bath, while being stirred with the rate of 250-350rpm/min, side addition
The NaOH solution of 2.5-3.5wt% adjusts pH to 8-9, after modifying agent is added dropwise, adds NaOH solution for the pH of system and is maintained at 8-
9, it adds 4 times repeatedly, the total addition level of modifying agent is the 8-12wt%, reaction time 50-70min of nano-cellulose quality
After obtain modified nanometer cellulose；The modifying agent is acid anhydrides.
Hydroxyl rich on nano-cellulose molecule, can generate Hydrogenbond abundant, but excessive hydroxyl
Also negative effect is brought：The hydrophily of composite membrane is excessively high.After the fermentation process of above-mentioned Mixed Microbes, by the work of microorganism
With, the hydroxyl on a part of nano-cellulose can be reduced, it is then twice-modified to nano-cellulose with modifying agent, with further
Adjust the hydrophobicity of nano-cellulose.
Preferably, the nanoclay inorganic particulate passes through modification：By nanoclay inorganic particulate and its 0.1-
The water mixing of the Cetyltrimethylammonium bromide of 0.3 times of quality, 4-6 times of quality, stirs evenly, is heated to 35-45 DEG C, ball milling
Solid is cleaned then after being centrifuged, filtering, is dry by 40-80min.
Nanoclay inorganic particulate is rendered as the laminar structured of Close stack on microcosmic, therefore nanoclay is inorganic
The dispersibility of particle is poor, and agglomeration is easy to happen when being added in aqueous solution.In the present invention, if nanoclay is inorganic
Particle can not be uniformly dispersed, and the uniformity that will cause film forming is deteriorated.For this purpose, present invention Cetyltrimethylammonium bromide is to receiving
Rice clay mineral particle is modified, and in modifying process, Cetyltrimethylammonium bromide can be with the inorganic grain of nanoclay
Son carry out ion exchange, intert into nanoclay inorganic particulate interlayer, adjacent layer structure is strutted, increase lamella it
Between spacing, improve nanoclay inorganic particulate dispersibility in water.It is subsequent mixed with nano-cellulose and PVA after, nanometer
Cellulose and PVA are able to enter its interlayer and form three-dimension interaction network, not only further increase the piece of nanoclay inorganic particulate
Interlamellar spacing, and the nanoclay inorganic particulate of single layer can also be locked between complicated three-dimensional net structure, it will receive accordingly
The barrier property of rice clay mineral particle performs to ultimate attainment.
Preferably, nano-cellulose/PVA/ nanoclay complex liquid can also add organic water-fast rush of 0.2-0.4wt%
The preparation method of stick, organic MR adhesive is as follows：By resin compound, the diphenol at least containing two epoxy groups
Base propane is mixed, and is then added cyclohexanone as solvent, is added triphenylbut base bromide phosphine as catalyst, be heated to
130-150 DEG C, react 1-3h, finally filtered, dry after organic MR adhesive is made；Wherein at least containing there are two epoxy groups
The molar ratio of phenolic hydroxyl group is 1: 1.3-1.5 in the resin compound epoxy group and diphenol propane of group.
Organic water-fast cohesive promoting agent prepared by the present invention has the characteristics that adhesiveness, water resistance are all good, can enhance composite membrane
The degree of cross linking and water resistance.Organic water-fast cohesive promoting agent of the invention contains excessive phenolic hydroxyl group during the preparation process, can with receive
Hydrogenbond occurs for rice cellulose, polyvinyl alcohol, forms three-dimensional net structure.
It is compared with the prior art, the beneficial effects of the invention are as follows：
(1) the raw material PVA and nano-cellulose used has the performance of green fully biodegradable, and nanoclay then belongs to nothing
Machine particle, not can cause environmental pollution, and be entirely a kind of green environment friendly composite material.
(2) nano-cellulose and nanoclay are nanoscales, and addition will not generate the light transmission of composite membrane
Larger impact.
(3) the uniform and fibril with nanoscale of nano-cellulose can form the network structure of intensive complexity, increase oxygen
Gas molecule penetrates path (as shown in Figure 1), while the addition of nanoclay can further promote the barrier property of composite film material
Can, so that its OTR oxygen transmission rate the decline of the order of magnitude is occurred；The hydroxyl group on nano-cellulose can be with the hydroxyl on PVA simultaneously
Group forms Hydrogenbond, effectively promotes the strength character of composite membrane.
(4) subsequent chloride treatment conditions are mild, easy to operate, can effectively improve the vapor resistance of composite film material
Separating performance.
(5) composite film material prepared by the present invention not only has excellent oxygen and vapor water barriers performance, mechanical property
Can and good biodegradability, and light transmittance is up to 89%, makes it can in food fresh keeping packaging, Key works Drug packing, green
The fields such as degradable packing material have extensive commercial applications potential.
Detailed description of the invention
Fig. 1 is the schematic illustration that nano-cellulose increases that oxygen molecule penetrates path；
Fig. 2 is pure PVA film and nano-cellulose/PVA/ nanoclay composite membrane determination of light transmittance result.
Specific embodiment
The present invention will be further described with reference to the examples below.
Total embodiment
A kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film, includes the following steps：
1) taking concentration is that the nano-cellulose gel of 0.5-1.5wt% is added to the water, and being configured to concentration is 0.1~0.8wt%
Nano-cellulose solution, 5~15min of decentralized processing at 10000~15000r/min.
2) it takes nanoclay inorganic particulate to be added to the water, is formulated as the nanoclay suspension of 0.5~5wt% of concentration,
2~6h of decentralized processing at 10000~15000r/min.
3) it takes solid PVA soluble in water, is formulated as the PVA solution of concentration 5-10wt%, nano-cellulose point is then added
Dispersion liquid, heating stirring mixes 1~3h in 90~100 DEG C of water-baths, and nanoclay suspension is then added, continues to be stirred 2
~4h obtains nano-cellulose/PVA/ nanoclay complex liquid, wherein the quality accounting of PVA, nano-cellulose, nanoclay
It is 70~98: 1~15: 1~15.
4) by nano-cellulose/PVA/ nanoclay complex liquid, standing and defoaming handles 4~8h at room temperature, pours into polystyrene
Levelling in plastic mould, vacuum drying, obtains the composite membrane with a thickness of 50-100 μm；Wherein, 40~60 DEG C of drying temperature, vacuum
Degree -0.1MPa, 3~5d of time.
5) laminated film is placed in 2~4min of impregnation in acyl chlorides/petroleum ether mixed liquor of 1~3wt%, be then put in
2~6min is reacted at 100-110 DEG C.
Wherein, the nano-cellulose be receive fibrillated fibers element, nano micro crystal cellulose, in Nano bacteria cellulose at least
Have one-dimensional having a size of nanoscale cellulose；The nanoclay is bentonite, kaolin or vermiculite.The degree of polymerization of the PVA
Between 600~2500, alcoholysis degree is between 80%~98%.The acyl chlorides is fat acyl chloride or caproyl chloride.
Optionally, the nano-cellulose passes through modification：By nano-cellulose be added to its 8-12 times of quality, contain
There are lactic acid bacteria, photosynthetic bacteria and saccharomycete and total bacteria concentration is to be heated to 30-40 DEG C, hair in the mixed bacteria liquid of 0.01-0.02wt%
Ferment 1-2 days；Then nano-cellulose is made into aqueous solution, the NaOH solution of 3-5mol/L is added dropwise while stirring, adjust pH into
Property；It is subsequently placed in 25-35 DEG C of water-bath, while being stirred with the rate of 250-350rpm/min, 2.5-3.5wt%'s added in side
NaOH solution adjusts pH to 8-9, after modifying agent is added dropwise, adds NaOH solution for the pH of system and is maintained at 8-9, add repeatedly
4 times, the total addition level of modifying agent is the 8-12wt% of nano-cellulose quality, obtains modified Nano after reaction time 50-70min
Cellulose；The modifying agent is acid anhydrides.
Optionally, the nanoclay inorganic particulate passes through modification：By nanoclay inorganic particulate and its 0.1-0.3
The water mixing of the Cetyltrimethylammonium bromide of times quality, 4-6 times of quality, stirs evenly, is heated to 35-45 DEG C, ball milling 40-
Solid is cleaned then after being centrifuged, filtering, is dry by 80min.
Optionally, organic water-fast rush that nano-cellulose/PVA/ nanoclay complex liquid can also add 0.2-0.4wt% is glued
The preparation method of agent, organic MR adhesive is as follows：By resin compound, the diphenylol at least containing two epoxy groups
Propane is mixed, and is then added cyclohexanone as solvent, is added triphenylbut base bromide phosphine as catalyst, be heated to 130-
150 DEG C, react 1-3h, finally filtered, dry after organic MR adhesive is made；Wherein at least containing there are two epoxy groups
The molar ratio of phenolic hydroxyl group is 1: 1.3-1.5 in resin compound epoxy group and diphenol propane.
Embodiment 1
1) preparation of nano-cellulose aqueous dispersions：
Nano-cellulose (fibrillated fibers of receiving are plain) gel that 200g concentration is 1% is taken to be added in the deionized water of 200g, prepare
At concentration be 0.5% nano-cellulose solution, using high speed disperser 10000r/min revolution decentralized processing 15min.
2) preparation of nanoclay suspension：Take 10g nanoclay inorganic particulate (bentonite) be added to 200g go from
In sub- water, it is configured to the nanoclay suspension that concentration is 0.5%, is dispersed under 10000r/min revolution using high speed disperser
Handle 2h.
3) nano-cellulose/PVA/ nanoclay complex liquid preparation：Weighing 8g solid PVA, (degree of polymerization is 600~2500
Between, alcoholysis degree is between 80%~98%) it is dissolved in the deionized water of 100g, a certain proportion of nano-cellulose is then added
Aqueous dispersions are placed in heating stirring in 90 DEG C of thermostat water baths and mix 2h, a certain proportion of nanoclay suspension is then added,
Continue to be stirred 4h, obtains nano-cellulose/PVA/ nanoclay complex liquid of different ratio mixing, wherein PVA, Nanowire
Tie up element, the quality accounting of nanoclay is 70: 15: 15.
4) nano-cellulose/PVA/ nanoclay laminated film preparation：By nano-cellulose/PVA/ in step (3)
Standing and defoaming handles 4h to nanoclay complex liquid at room temperature, pours into levelling in polystyrene plastics mold, dry using constant-temperature vacuum
Dry case carries out the drying of composite film material, 40 DEG C of drying condition, vacuum degree -0.1MPa, the time 3 days, prepare nano-cellulose/
PVA/ nanoclay laminated film, film thickness are 50 μm.
5) the chloride processing of laminated film：4) the middle laminated film prepared is placed in 1% fat acyl chloride/petroleum ether to mix
In liquid after impregnation 2min, 105 DEG C of reaction 2min in constant temperature blast drying oven are subsequently placed into, the chloride of laminated film is completed
Hydrophobic treatment.
Embodiment 2
A kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film, includes the following steps：
1) acetobacter xylinum strain is seeded in seed culture medium, clogs bottleneck with sterilized cotton, jiggles, make seed
Dispersion in the medium, is then cultivated 3 days in 25 DEG C of constant incubators.Activated bacterial strain access slant medium is taken,
30 DEG C in constant-temperature table, 150rpm shaken cultivation 24 hours.The fermentation medium of the cultured seed access 200mL of 15mL is taken again
In, fully shake, make strain separating and it is fully dispersed in the fermentation medium, then 30 DEG C in constant-temperature table, 150rpm vibration
Culture 7 days is swung, bacteria cellulose film is obtained.Bacteria cellulose film is taken out from fermentation medium, is rinsed through filtering, deionized water
Afterwards, it is immersed in 4%NaOH solution, 1h is heated in 100 DEG C of boiling water baths, remove residual media and mycoprotein, then use
Dilute hydrochloric acid neutralizes, then is rinsed with deionized water to neutrality and obtain Nano bacteria cellulose.Taking concentration is the bacteria nano of 0.5wt%
Cellulose is added to the water, and is configured to the nano-cellulose solution that concentration is 0.1wt%, the decentralized processing at 12500r/min
10min。
Wherein, the seed culture medium and fermentation medium group become：Glucose 5w/v%, peptone 0.5w/v%, lemon
Lemon acid 0.1w/v%, disodium hydrogen phosphate 0.2w/v%, potassium dihydrogen phosphate 0.1w/v%, yeast extract 0.5w/v%；The inclined-plane training
The group for supporting base becomes：Glucose 5w/v%, peptone 0.5w/v%, citric acid 0.1w/v%, agar 2.0w/v%, calcium carbonate
0.05w/v%.PH=6.0 ± 0.2 of above-mentioned culture medium, sterilize 30min at 121 DEG C, 0.1MPa.
The present embodiment targetedly uses above-mentioned dynamic three for the concrete application of Nano bacteria cellulose in the present invention
Segmentation cultivation fermented-producing bacteria nano-cellulose, the Nano bacteria cellulose cultivated be " flakes ", i.e., every
Adhere to very much " lint shape " tiny staple fibers around long principal fiber cellulose fiber, the diameter and length of these cellulose fibres are not
Equally, be conducive to the connection between reinforcing fiber, promote the formation of network-like connection, improve the strength character of composite membrane.Meanwhile
This method is easy to operate, and yield is higher, can be realized continuous production, adapts to industrialized production requirement.
2) nanoclay inorganic particulate (kaolin) is taken to be added to the water, the nanoclay for being formulated as concentration 0.5wt% is outstanding
Supernatant liquid, the decentralized processing 4h at 12500r/min.
3) it takes solid PVA (for the degree of polymerization between 600~2500, alcoholysis degree is between 80%~98%) soluble in water, matches
It is made as the PVA solution of concentration 5wt%, nano-cellulose dispersion liquid is then added, heating stirring mixes 3h in 90 DEG C of water-baths, with
Nanoclay suspension is added afterwards, continues to be stirred 2h, obtains nano-cellulose/PVA/ nanoclay complex liquid, wherein
PVA, nano-cellulose, nanoclay quality accounting be 85: 7.5: 7.5.
4) by nano-cellulose/PVA/ nanoclay complex liquid, standing and defoaming handles 6h at room temperature, pours into polystyrene modeling
Expect levelling in mold, vacuum drying obtains the composite membrane with a thickness of 75 μm；Wherein, 50 DEG C of drying temperature, vacuum degree -0.1MPa,
Time 4d.
5) laminated film is placed in impregnation 3min in caproyl chloride/petroleum ether mixed liquor of 2wt%, is then put in 110
2min is reacted at DEG C.
Wherein, the nano-cellulose passes through modification：By nano-cellulose be added to its 10 times of quality, containing cream
Sour bacterium, photosynthetic bacteria and saccharomycete and total bacteria concentration are to be heated to 35 DEG C in the mixed bacteria liquid of 0.015wt%, are fermented 1.5 days；So
Nano-cellulose is made into aqueous solution afterwards, the NaOH solution of 4mol/L is added dropwise while stirring, adjusts pH to neutrality；It is subsequently placed in 30
DEG C water-bath in, while being stirred with the rate of 300rpm/min, the NaOH solution that 3wt% is added on side adjusts pH to 8.5, is added dropwise and is modified
After agent, NaOH solution being added by the pH of system and is maintained at 8.5, is added 4 times repeatedly, the total addition level of modifying agent is Nanowire
The 10wt% of quality amount is tieed up, obtains modified nanometer cellulose after reaction time 60min；The modifying agent is acetic anhydride.
The nanoclay inorganic particulate passes through modification：By the octadecyl three of nanoclay and its 0.2 times of quality
The water mixing of methyl bromide ammonium, 5 times of quality, stirs evenly, is heated to 40 DEG C, ball milling 60min, then after being centrifuged, filtering,
Solid is cleaned, is dry.
Embodiment 3
A kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film, includes the following steps：
1) taking concentration is that nano-cellulose (nano micro crystal cellulose) gel of 1.5wt% is added to the water, and being configured to concentration is
The nano-cellulose solution of 0.8wt%, the decentralized processing 5min at 15000r/min.
2) it takes nanoclay inorganic particulate (vermiculite) to be added to the water, is formulated as the nanoclay suspension of concentration 5wt%,
The decentralized processing 2h at 15000r/min.
3) it takes solid PVA (for the degree of polymerization between 600~2500, alcoholysis degree is between 80%~98%) soluble in water, matches
It is made as the PVA solution of concentration 10wt%, nano-cellulose dispersion liquid is then added, heating stirring mixes 3h in 90 DEG C of water-baths,
Nanoclay suspension is then added, continues to be stirred 4h, obtains nano-cellulose/PVA/ nanoclay complex liquid, wherein
PVA, nano-cellulose, nanoclay quality accounting be 98: 1: 1.
4) by nano-cellulose/PVA/ nanoclay complex liquid, standing and defoaming handles 4h at room temperature, pours into polystyrene modeling
Expect levelling in mold, vacuum drying obtains the composite membrane with a thickness of 50 μm；Wherein, 40 DEG C of drying temperature, vacuum degree -0.1MPa,
Time 5d.
5) laminated film is placed in impregnation 4min in caproyl chloride/petroleum ether mixed liquor of 3wt%, is then put in 100
6min is reacted at DEG C.
Wherein, the nano-cellulose passes through modification：By nano-cellulose be added to its 8 times of quality, containing cream
Sour bacterium, photosynthetic bacteria and saccharomycete and total bacteria concentration are to be heated to 30 DEG C in the mixed bacteria liquid of 0.01wt%, are fermented 2 days；Then will
Nano-cellulose is made into aqueous solution, and heating temperature is added the stirring of 0.05g ammonium persulfate initiator and is warming up to 70 DEG C, be added to 50 DEG C
3.5g acrylic monomers, insulation reaction 2h then heat to 80 DEG C, insulation reaction 4h.After reaction by nano-cellulose water
Solution is dialysed 3~4d in the deionized water of flowing, removes unreacted acrylic monomers, complete nano-cellulose it is modified at
Reason；The modifying agent is acrylic acid.
The nanoclay inorganic particulate passes through modification：By the octadecyl three of nanoclay and its 0.1 times of quality
The water mixing of methyl bromide ammonium, 4 times of quality, stirs evenly, is heated to 35 DEG C, ball milling 80min, then after being centrifuged, filtering,
Solid is cleaned, is dry.
Embodiment 4
The present embodiment and embodiment 3 the difference is that, the present embodiment nano-cellulose/PVA/ nanoclay complex liquid also
Organic water-fast cohesive promoting agent added with 0.3wt%, the preparation method of organic MR adhesive are as follows：Two will at least be contained
Resin compound, the diphenol propane of epoxy group are mixed, and are then added cyclohexanone as solvent, are added triphenyl butyl
Bromide phosphine is heated to 140 DEG C as catalyst, reacts 2h, finally filtered, dry after organic MR adhesive is made；Wherein
The molar ratio of phenolic hydroxyl group is 1: 1.4 in the resin compound epoxy group and diphenol propane of epoxy group at least containing there are two.
The measurement of light transmittance
The measurement of nano cellulose composite film light transmittance uses the ultraviolet-uisible spectrophotometer for being furnished with pellicle fixture, the wave of measurement
Long range is 200nm to 1000nm, scanning speed 300nm/min, sampling interval 1nm, and spectral bandwidth 4nm changes lamp wavelength
340nm measures 25 DEG C of temperature, sensitivity 100%.Obtained nano cellulose composite film is taken to be placed in UV-visible spectrometer sample
In product slot, for ensure test accuracy, each sample duplicate measurements 3 times, as a result as shown in Figure 2.
As shown in Figure 2, nano-cellulose/light transmittance of PVA/ nanoclay composite membrane and the light transmittance curve of pure PVA film
It is almost overlapped, especially in the visible light region of 400nm or more, nano-cellulose/PVA/ nanoclay composite membrane light transmittance
(89%) and the light transmittance of pure PVA film (90%) is close, it is seen that it has very good translucency, can be used for food and medicine
Product fresh-keeping packaging.
The measurement of oxygen barrier property and vapor water barriers performance
The oxygen barrier property of composite film material and the measurement result of vapor water barriers performance are as shown in table 2 and table 3.Therefrom may be used
Know, nano-cellulose/PVA/ nanoclay OTR oxygen transmission rate the order of magnitude occurs compared to the OTR oxygen transmission rate of pure PVA film
Decline, the laminated film for being added to nano-cellulose and nanoclay has very excellent oxygen barrier property, Ji Huke
With (transmitance data are shown in Table 2 annotations with the oxygen high-isolation film such as widely applied PVDC and EVOH compares favourably currently on the market
Place).This, which has benefited from nano-cellulose and nanoclay, can act synergistically to form fine and close network structure, increase oxygen molecule and penetrate
Crooked route, while film, after chloride is handled, vapor water barriers performance also has order of magnitude promotion, and effect is obvious.
Nano-cellulose group compound film prepared by the present invention has excellent oxygen, vapor water barriers energy and good light transmission
Performance, it can be achieved that its food fresh keeping, Key works Drug packing, degradable green packaging etc. fields commercial applications.
The OTR oxygen transmission rate measurement result of 2 laminated film of table
The measurement of 3 composite membrane moisture-vapor transmission of table
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；It is used in the present invention
Method is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (10)
1. a kind of preparation method of degradable green high-barrier high grade of transparency nano cellulose composite film, it is characterised in that including with
Lower step：
1）Nano-cellulose gel is added to the water dilution, decentralized processing obtains nano-cellulose aqueous dispersions；
2）Nanoclay inorganic particulate is added to the water, decentralized processing obtains nanoclay suspension；
3）PVA solution is prepared, nano-cellulose dispersion liquid is then added, heating stirring mixing is then added nanoclay and suspends
Liquid continues to be stirred, and obtains nano-cellulose/PVA/ nanoclay complex liquid；
4）To nano-cellulose/PVA/ nanoclay complex liquid standing and defoaming processing, levelling in mold is poured into, is dried in vacuo, system
Obtain nano-cellulose/PVA/ nanoclay composite membrane；
5）Composite membrane is placed in impregnation in acyl chlorides/petroleum ether mixed liquor, then heating reaction, completes the chloride of composite membrane
Hydrophobic treatment.
2. a kind of preparation side of degradable green high-barrier high grade of transparency nano cellulose composite film as described in claim 1
Method, which is characterized in that step 1）Specially：Taking concentration is that the nano-cellulose gel of 0.5-1.5wt% is added to the water, and is prepared
The nano-cellulose solution for being 0.1 ~ 0.8wt% at concentration, 5 ~ 15min of decentralized processing at 10000 ~ 15000r/min.
3. a kind of preparation side of degradable green high-barrier high grade of transparency nano cellulose composite film as claimed in claim 2
Method, which is characterized in that step 2）Specially：It takes nanoclay inorganic particulate to be added to the water, is formulated as 0.5 ~ 5wt%'s of concentration
Nanoclay suspension, 2 ~ 6h of decentralized processing at 10000 ~ 15000r/min.
4. a kind of preparation side of degradable green high-barrier high grade of transparency nano cellulose composite film as claimed in claim 3
Method, which is characterized in that step 3）Specially：It takes solid PVA soluble in water, is formulated as the PVA solution of concentration 5-10wt%, then
Nano-cellulose dispersion liquid is added, heating stirring mixes 1 ~ 3h in 90 ~ 100 DEG C of water-baths, nanoclay suspension is then added,
Continue to be stirred 2 ~ 4h, obtain nano-cellulose/PVA/ nanoclay complex liquid, wherein PVA, nano-cellulose, nanometer are viscous
The quality accounting of soil is 70 ~ 98:1~15:1~15.
5. a kind of degradable green high-barrier high grade of transparency nano cellulose composite film as claimed in claim 1 or 2 or 3 or 4
Preparation method, which is characterized in that step 4）Specially：Nano-cellulose/PVA/ nanoclay complex liquid is stood at room temperature
Deaeration handles 4 ~ 8h, pours into levelling in polystyrene plastics mold, is dried in vacuo, obtains the composite membrane with a thickness of 50-100 μm；
Wherein, 40 ~ 60 DEG C of drying temperature, vacuum degree -0.1MPa, 3 ~ 5d of time.
6. a kind of degradable green high-barrier high grade of transparency nano cellulose composite film as claimed in claim 1 or 2 or 3 or 4
Preparation method, which is characterized in that step 5）Specially：Laminated film is placed in acyl chlorides/petroleum ether mixed liquor of 1 ~ 3wt%
2 ~ 4min of impregnation is then put in 2 ~ 6min of reaction at 100-110 DEG C.
7. a kind of system of degradable green high-barrier high grade of transparency nano cellulose composite film as described in claims 1 or 2 or 3
Preparation Method, which is characterized in that the nano-cellulose is to receive fibrillated fibers element, nano micro crystal cellulose, Nano bacteria cellulose
Middle at least one dimension is having a size of nanoscale cellulose；The nanoclay is bentonite, kaolin or vermiculite.
8. a kind of preparation of degradable green high-barrier high grade of transparency nano cellulose composite film as described in claim 1 or 4
Method, which is characterized in that the degree of polymerization of the PVA is between 600 ~ 2500, and alcoholysis degree is between 80% ~ 98%.
9. a kind of preparation side of degradable green high-barrier high grade of transparency nano cellulose composite film as described in claim 1
Method, which is characterized in that the acyl chlorides is fat acyl chloride or caproyl chloride.
10. a kind of preparation side of degradable green high-barrier high grade of transparency nano cellulose composite film as described in claim 1
Method, which is characterized in that step 1）In, the nano-cellulose passes through modification：Nano-cellulose is added to its 8-12 times
Quality, containing lactic acid bacteria, photosynthetic bacteria and saccharomycete and total bacteria concentration is to be heated in the mixed bacteria liquid of 0.01-0.02wt%
It 30-40 DEG C, ferments 1-2 days；Then nano-cellulose is made into aqueous solution, the NaOH solution of 3-5 mol/L is added dropwise while stirring,
PH is adjusted to neutrality；It is subsequently placed in 25-35 DEG C of water-bath, while being stirred with the rate of 250-350rpm/min, 2.5- is added on side
The NaOH solution of 3.5wt% adjusts pH to 8-9, after modifying agent is added dropwise, adds NaOH solution for the pH of system and is maintained at 8-9, so
It adds 4 times repeatedly, the total addition level of modifying agent is the 8-12wt% of nano-cellulose quality, is obtained after reaction time 50-70min
Modified nanometer cellulose；The modifying agent is acid anhydrides.
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