CN116356607A - High-barrier cellulose-based paper packaging material and preparation method and application thereof - Google Patents
High-barrier cellulose-based paper packaging material and preparation method and application thereof Download PDFInfo
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- CN116356607A CN116356607A CN202310182181.3A CN202310182181A CN116356607A CN 116356607 A CN116356607 A CN 116356607A CN 202310182181 A CN202310182181 A CN 202310182181A CN 116356607 A CN116356607 A CN 116356607A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 55
- 239000001913 cellulose Substances 0.000 title claims abstract description 55
- 239000005022 packaging material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 96
- 229920000742 Cotton Polymers 0.000 claims abstract description 78
- 244000198134 Agave sisalana Species 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 44
- 239000002002 slurry Substances 0.000 claims abstract description 44
- 238000004537 pulping Methods 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000011268 mixed slurry Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000008104 plant cellulose Substances 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 241000196324 Embryophyta Species 0.000 claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002159 nanocrystal Substances 0.000 claims abstract description 3
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 235000010980 cellulose Nutrition 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000010009 beating Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 14
- 238000013329 compounding Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 7
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 7
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 7
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 7
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 235000013399 edible fruits Nutrition 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000011122 softwood Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 235000021022 fresh fruits Nutrition 0.000 abstract description 3
- 239000000123 paper Substances 0.000 description 66
- 230000005540 biological transmission Effects 0.000 description 20
- 241000609240 Ambelania acida Species 0.000 description 16
- 239000010905 bagasse Substances 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 238000011002 quantification Methods 0.000 description 10
- 238000007731 hot pressing Methods 0.000 description 9
- 244000166124 Eucalyptus globulus Species 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 7
- 238000000502 dialysis Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000011624 Agave sisalana Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 230000016615 flocculation Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Paper (AREA)
- Wrappers (AREA)
Abstract
The invention discloses a high-barrier cellulose-based paper packaging material, and a preparation method and application thereof. The preparation method of the high-barrier cellulose-based paper packaging material comprises the following steps: (1) Pulping cotton fiber and sisal fiber respectively, then fully dispersing to obtain cotton fiber dispersion liquid and sisal fiber dispersion liquid, and uniformly mixing to obtain CF/SF mixed slurry; (2) Adding plant-based nanocellulose (plant cellulose nanofibrils and plant cellulose nanocrystals) into the CF/SF mixed slurry under the stirring condition to obtain CF/SF/NF compound slurry; (3) And (3) manufacturing and forming the CF/SF/NF compound slurry, and performing wet heat pressing treatment to obtain the high-barrier cellulose-based paper packaging material. The material obtained by the invention has good mechanical property and barrier property, and can be used for packaging fresh-keeping materials of fresh fruits.
Description
Technical Field
The invention relates to the technical field of packaging materials, in particular to a high-barrier cellulose-based paper packaging material, and a preparation method and application thereof.
Background
Fresh fruits can be in contact with oxygen or water molecules when stored in common packages, and are easy to spoil and deteriorate, so that the shelf life of the fruits is shortened. The development of the high-barrier packaging material can protect packaged fruits and prolong the shelf life of the fruits. According to the statistics of the world packaging association, the current packaging materials mainly comprise materials such as plastics, glass, paper and metal, and from the standpoint of carbon footprint, paper-based packaging materials (paper packaging materials) are more advantageous than traditional plastic, glass or metal packaging. In addition, the paper packaging material prepared from the degradable bio-based material is portable and convenient to transport, and the paper packaging material can be naturally degraded or recycled, so that the paper packaging material has obvious environmental protection advantages.
At present, in order to improve the barrier property of paper, a process of adding chemical additives or coating chemicals into slurry is generally adopted, and although the barrier purpose can be achieved, the chemical reagents have the defects of high cost, toxicity and the like, and do not accord with the concept of sustainable development. Cellulose is a natural polymer material with abundant reserves in nature, has the advantages of low price, biodegradability, environmental protection and the like, and is widely applied to the fields of food, chemical industry, biology and the like. However, the paper formed by the common paper pulp fiber has rough and porous surface, oxygen and water molecules can easily pass through, the barrier property is poor, and the paper is difficult to be directly applied to high-barrier packaging materials.
Disclosure of Invention
The invention aims at overcoming the defects and shortcomings of the prior art and providing a preparation method of a high-barrier cellulose-based paper wrapping material.
The invention further aims at providing the high-barrier cellulose-based paper packaging material prepared by the method.
It is a further object of the present invention to provide the use of the high barrier cellulose-based paper wrapper.
The aim of the invention is achieved by the following technical scheme:
the preparation method of the high-barrier cellulose-based paper packaging material comprises the following steps:
(1) Compounding long fiber slurry: pulping Cotton Fiber (CF) and Sisal Fiber (SF) respectively, then fully dispersing to obtain cotton fiber dispersion liquid and sisal fiber dispersion liquid, and uniformly mixing the cotton fiber dispersion liquid and the sisal fiber dispersion liquid to obtain CF/SF mixed slurry;
(2) Wet end addition of nanocellulose: adding plant-based Nanocellulose (NF) into the CF/SF mixed slurry obtained in the step (1) under the stirring condition, and uniformly mixing to obtain CF/SF/NF compound slurry; wherein the plant-based Nanocellulose (NF) is a plant Cellulose Nanofibrillar (CNF) and a plant Cellulose Nanocrystalline (CNC);
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2), and performing wet heat pressing treatment to obtain the high-barrier cellulose-based paper packaging material.
And (3) pulping in the step (1) by adopting a PFI mill.
The length of the cotton fiber in the step (1) is 25-38 mm, and the diameter is 7-20 mu m; sisal fibers have a length of 13 to 22mm and a diameter of 33 to 48 μm.
The beating revolution of the cotton fiber in the step (1) is 5000-8000 revolutions, the beating concentration is 2.0-4.0%, and the beating degree is 50-70 DEG SR; the beating revolution of the sisal fiber is 8000-10000 revolutions, the beating concentration is 2.0-3.0%, and the beating degree is 40-50 DEG SR.
Dispersing cotton fibers in the dispersing treatment in the step (1) in an electric dispersing machine with the rotating speed of 4000-6000 r/min for 15-25 min at the concentration of 1.5-2.0% by mass percent; the sisal fibers are dispersed for 10 to 20 minutes in an electric dispersing machine with the rotating speed of 5000 to 8000r/min at the concentration of 1.0 to 3.0 percent by mass percent.
The mass ratio of the cotton fibers in the cotton fiber dispersion liquid and the sisal fibers in the sisal fiber dispersion liquid in the step (1) is (4-6): (5-7).
The diameter of the plant cellulose nanofibrils in the step (2) is 20-60 nm, and the length is 300-800 nm (preferably 335-800 nm); preferably, the preparation method comprises the steps of taking softwood pulp as a raw material, and preparing the softwood pulp by mechanical grinding and high-pressure homogenization; wherein, the conditions of mechanical grinding are as follows: grinding 10 times under 0 and-50 μm gap, with rotation speed of 1200rpm; then the clearance of the grinding disc is adjusted to-100 mu m for grinding for 20 times, and the rotating speed is 1800rpm; the conditions of high-pressure homogenization are as follows: the temperature is 25 ℃, the operating pressure is 150MPa, and the cycle is 3 times.
The diameter of the plant cellulose nanocrystalline in the step (2) is 10-20 nm, and the length is 150-250 nm; preferably, the preparation method takes microcrystalline cellulose as a raw material and is prepared by organic acid hydrolysis: adding microcrystalline cellulose into maleic acid solution, stirring for hydrolysis at 40+ -5deg.C, adding water to terminate acid hydrolysis reaction, centrifuging for washing, collecting lower layer solid, dialyzing, and collecting upper layer light blue solution for rotary evaporation concentration to obtain CNC suspension.
The concentration mass percentage of the maleic acid solution is 30-40%; preferably 35% by mass.
The solid-to-liquid ratio of the microcrystalline cellulose to the maleic acid solution is 1: 15-30 g/mL; preferably 1:20 g/mL.
The added water is 8-10 times of the volume of the added system; preferably 10 volumes of water are added to the system.
The dialysis is to adopt a dialysis bag with the molecular weight cut-off of 8000-12000 Da for 7-10 days, wherein the dialysate is water.
The concentration of the plant-based nanocellulose in the step (2) is 5.0-7.0% by mass.
The addition amount of the plant-based nanocellulose in the step (2) is 1.0-8.0% of the mass of the CF/SF/NF compound slurry.
The mass ratio of the plant cellulose nanofibrils to the plant cellulose nanocrystals in the step (2) is (1-2): (6-8).
The stirring rotating speed in the step (2) is 4000-6000 r/min.
And (3) the paper making and forming is carried out by adopting an inclined wire paper machine.
The concentration of the CF/SF/NF compound slurry in the step (3) is 0.06-0.15% by mass.
The wet and hot pressure conditions in the step (3) are as follows: the temperature is 80-95 ℃, the pressure is 16-18 MPa, and the time is 15-30 min.
A high barrier cellulose-based paper wrapper prepared by any one of the preparation methods described above.
The performance indexes of the high-barrier cellulose base paper packaging material are as follows: quantification: 55-60 g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 2.8-4.2 kN/m; tear strength: 215.3 to 234.7mN; oxygen transmission rate: 2.4-4.7 cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 135-162 g/m 2 ·day。
The high-barrier cellulose-based paper wrapper is applied to packaging materials.
The packaging material comprises a packaging fresh-keeping material; preferably a packaging and fresh-keeping material for fresh and/or fruit.
Compared with the prior art, the invention has the following advantages and effects:
(1) The cotton fiber, sisal fiber, cellulose nanofibril and cellulose nanocrystalline used in the invention are all degradable biological base materials, and the all-cellulose base paper wrapping material prepared from the raw materials can be naturally degraded or recycled, belongs to high-performance environment-friendly packaging materials, and can be used for packaging fresh-keeping materials of fresh fruits by using paper instead of plastic.
(2) The high-barrier cellulose-based paper packaging material prepared by the invention is obtained by reasonably compounding four fiber raw materials, and fully utilizes the advantages of different fibers: sisal fibers are long and high in strength, and the physical strength of finished paper can be remarkably improved; the cotton fibers are fine and soft, and can ensure the tight combination between the fibers; the plant-based nano cellulose has nano-scale, high length-diameter ratio and large specific surface area, and CNF and CNC have different sizes, can be well filled between cotton fibers and sisal fibers, improves the interfacial binding force between different fibers, enables long fibers and short fibers to be tightly connected, and improves the mechanical strength of cellulose paper.
(3) The invention adopts the wet forming technology of the ultra-low concentration inclined wire paper machine, can solve the problem of easy flocculation of fibers, realizes uniform dispersion and forming of long and short fibers under ultra-low concentration, and is beneficial to improving the mechanical properties of finished paper; meanwhile, wet hot pressing treatment is adopted to facilitate softening and interweaving of fibers, so that uniformity of cellulose paper is improved, various fibers in the paper base material are combined more tightly, and the paper has stronger toughness and compactness.
(4) According to the invention, through compounding plant-based long fibers and nanofibers with different dimensions, the advantages of the materials are fully brought into play, the preparation process is simple, the full-cellulose-based paper packaging material with high barrier and high mechanical properties is constructed, theoretical basis and application reference are provided for development of novel paper-based barrier materials, and the green packaging industry is promoted to realize low-carbon development.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The test methods for specific experimental conditions are not noted in the examples below, and are generally performed under conventional experimental conditions or under experimental conditions recommended by the manufacturer. The reagents and starting materials used in the present invention are commercially available unless otherwise specified.
1. The Cotton Fiber (CF) related in the embodiment of the invention is purchased from Shandong Asahi textile Co., ltd, and has the length of 25-38 mm and the diameter of 7-20 mu m; sisal Fibers (SF) are available from Chen Minuo rope Inc. and are 13-22 mm in length and 33-48 μm in diameter.
2. The plant Cellulose Nanofibrils (CNF) related in the embodiment of the invention are prepared by taking softwood pulp (purchased from Shandong Sun paper company Co., ltd.) as a raw material through mechanical grinding and high-pressure homogenization, and have the diameter of 20-60 nm and the length of 300-800 nm; wherein, mechanical grinding: grinding 10 times under 0 and-50 μm gap, with rotation speed of 1200rpm; then the clearance of the grinding disc is adjusted to-100 mu m for grinding for 20 times, and the rotating speed is 1800rpm; homogenizing under high pressure: the operation pressure is 150MPa, the cycle is carried out for 3 times, and the temperature is controlled at 25 ℃.
3. The plant Cellulose Nanocrystalline (CNC) related in the embodiment of the invention is prepared by taking microcrystalline cellulose (purchased from Sigma-Aldrich) as a raw material through organic acid hydrolysis, and has the diameter of 10-20 nm and the length of 150-250 nm; the CNC preparation process by organic acid hydrolysis is as follows: 40mL of a maleic acid solution with a concentration of 35% (w/v) was placed in a water bath. 2.0g of microcrystalline cellulose was accurately weighed and slowly added to the maleic acid solution and hydrolyzed with stirring at 40℃for 60min. Distilled water was then added in an amount of 10 times the volume to terminate the acid hydrolysis reaction. And then washing the solid by adopting a centrifugal separation method, removing the upper layer solution, continuously adding water to wash the solid sediment of the lower layer, and repeating the centrifugal washing process for a plurality of times until the upper layer solution becomes turbid. Collecting the solid at the lower layer, putting the solid into a dialysis bag (with the molecular weight cut-off of 8000-12000 Da) and placing the dialysis bag into clear water for dialysis (for 7-10 days), and finally, carrying out centrifugal separation treatment on the solid and the liquid in the dialysis bag again, collecting the light blue solution at the upper layer, and carrying out rotary evaporation concentration to obtain CNC suspension with different concentrations for later use.
2. The detection of various parameters related in the embodiment of the invention is carried out according to a national standard detection method and an industry standard, and specifically comprises the following steps:
(1) quantification (GB/T451.2-2002);
(2) tensile strength (GB/T453-2002);
(3) tear strength (GB/T455-2002);
(4) oxygen transmission rate (GB/T19789-2005);
(5) water vapor transmission rate (GB/T22921-2008).
Example 1
The embodiment provides a preparation method of a high-barrier cellulose-based paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: pulping cotton fiber (with the length of 33-38 mm and the diameter of 7-14 μm) in a PFI mill, wherein the pulping revolution is 5000 revolutions, the pulping concentration is 2.0wt% and the pulping degree is 50 DEG SR; sisal fibers (length of 18-22 mm, diameter of 33-38 μm) were beaten in a PFI mill at 8000 revolutions, at 2.0wt% beaten concentration and at 40 ° SR. Then dispersing cotton fiber in an electric dispersing machine with the rotating speed of 4000r/min for 15min at the concentration of 1.5 mass percent; sisal fibers were dispersed at a concentration of 1.0% by mass in an electric disperser at 5000r/min for 10min. Finally, the cotton fiber dispersion liquid and the sisal fiber dispersion liquid after the dispersion treatment are subjected to absolute dry mass ratio of 4:5 (i.e. mass ratio of cotton fibers in the cotton fiber dispersion to sisal fibers in the sisal fiber dispersion, the same applies hereinafter) to obtain a CF/SF mixed slurry solution.
(2) Wet end addition of nanocellulose: adding CNF/CNC suspension with the mass concentration of 5.0% into the CF/SF mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 4000 r/min) (the absolute dry mass ratio of CNF to CNC is 1:6, wherein the diameter of CNF is 20-53 nm, the length is 335-672 nm, the diameter of CNC is 12-17 nm, the length is 150-231 nm, and the addition amount of CNF/CNC is 1.0% of the total mixed slurry mass formed by CF/SF+CNF/CNC), so as to prepare the CF/SF/NF composite slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.06wt%, and performing wet hot pressing treatment for 15min at the temperature of 80 ℃ and the pressure of 16MPa to obtain the high-barrier cellulose-based paper packaging material.
The performance indexes of the high-barrier cellulose base paper packaging material prepared in the embodiment are as follows: quantification: 60g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 2.8kN/m; tear strength: 215.3mN; oxygen transmission rate: 4.7cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 162g/m 2 ·day。
Example 2
The embodiment provides a preparation method of a high-barrier cellulose-based paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: pulping cotton fiber (length is 30-35 mm, diameter is 9-16 μm) in a PFI mill, wherein the pulping revolution is 6000 revolutions, the pulping concentration is 3.0wt%, and the pulping degree is 55 DEG SR; sisal fibers (17-20 mm in length and 36-41 μm in diameter) were beaten in a PFI mill with a beaten revolution of 8500 revolutions, a beaten concentration of 2.5wt% and a beaten degree of 45 DEG SR. Then dispersing cotton fiber in an electric dispersing machine with the rotating speed of 5000r/min for 20min at the concentration of 2.0 mass percent; sisal fibers were dispersed at a concentration of 1.5% by mass in an electric disperser at a speed of 6000r/min for 15min. Finally, the cotton fiber dispersion liquid and the sisal fiber dispersion liquid after the dispersion treatment are subjected to absolute dry mass ratio of 4:7, uniformly mixing to obtain the CF/SF mixed slurry solution.
(2) Wet end addition of nanocellulose: adding CNF/CNC suspension with the mass concentration of 6.0% into the CF/SF mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 5000 r/min) (the absolute dry mass ratio of CNF to CNC is 1:7, wherein the diameter of CNF is 27-46 nm, the length is 481-800 nm, the diameter of CNC is 10-15 nm, the length is 163-217 nm, and the addition amount of CNF/CNC is 3.0% of the total mixed slurry mass formed by CF/SF+CNF/CNC), so as to prepare the CF/SF/NF composite slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.48wt%, and performing wet hot pressing treatment for 20min at the temperature of 85 ℃ and the pressure of 17MPa to obtain the high-barrier cellulose-based paper packaging material.
The performance indexes of the high-barrier cellulose base paper packaging material prepared in the embodiment are as follows: quantification: 58g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 3.3kN/m; tear strength: 220.4mN; oxygen transmission rate: 4.2cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 154g/m 2 ·day。
Example 3
The embodiment provides a preparation method of a high-barrier cellulose-based paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: pulping cotton fiber (length of 27-32 mm, diameter of 13-18 μm) in PFI mill, wherein the pulping revolution is 7000 revolutions, the pulping concentration is 3.5wt%, and the pulping degree is 60 DEG SR; sisal fibers (15-19 mm in length and 38-44 μm in diameter) were beaten in a PFI mill with a beaten revolution of 9000 revolutions, a beaten concentration of 2.5wt% and a beaten degree of 50 DEG SR. Then dispersing cotton fiber in an electric dispersing machine with the rotating speed of 5000r/min for 20min at the concentration of 1.8 mass percent; sisal fibers were dispersed at a concentration of 2.0% by mass in an electric disperser at a speed of 7000r/min for 18min. Finally, the cotton fiber dispersion liquid and the sisal fiber dispersion liquid after the dispersion treatment are subjected to absolute dry mass ratio of 6:5, uniformly mixing to obtain the CF/SF mixed slurry solution.
(2) Wet end addition of nanocellulose: adding CNF/CNC suspension with the mass concentration of 6.5% (the absolute dry mass ratio of CNF to CNC is 2:7) into the CF/SF mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 6000 r/min), wherein the CNF diameter is 32-60 nm, the length is 372-725 nm, the CNC diameter is 13-18 nm, the length is 182-250 nm, and the CNF/CNC addition amount is 5.0% of the total mixed slurry mass formed by CF/SF+CNF/CNC, so as to prepare the CF/SF/NF composite slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.92wt%, and performing wet hot pressing treatment for 25min at the temperature of 90 ℃ and the pressure of 17MPa to obtain the high-barrier cellulose-based paper packaging material.
The performance indexes of the high-barrier cellulose base paper packaging material prepared in the embodiment are as follows: quantification: 56g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 3.7kN/m; tear strength: 227.8mN; oxygen transmission rate: 3.5cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 143g/m 2 ·day。
Example 4
The embodiment provides a preparation method of a high-barrier cellulose-based paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: pulping cotton fiber (with the length of 25-31 mm and the diameter of 15-20 μm) in a PFI mill, wherein the pulping revolution is 8000 revolutions, the pulping concentration is 4.0wt% and the pulping degree is 70 DEG SR; sisal fibers (length 13-17 mm, diameter 41-48 μm) were beaten in a PFI mill with a beaten revolution of 10000 revolutions, beaten concentration of 3.0wt% and beaten degree of 50 DEG SR. Then dispersing cotton fiber in an electric dispersing machine with the rotating speed of 6000r/min for 25min at the concentration of 2.0 mass percent; sisal fibers were dispersed at a concentration of 3.0% by mass in an electric disperser at a speed of 8000r/min for 20min. Finally, the cotton fiber dispersion liquid and the sisal fiber dispersion liquid after the dispersion treatment are subjected to absolute dry mass ratio of 6:7, uniformly mixing to obtain the CF/SF mixed slurry solution.
(2) Wet end addition of nanocellulose: adding a CNF/CNC suspension with the mass concentration of 7.0% into the CF/SF mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 6000 r/min) (the absolute dry mass ratio of CNF to CNC is 2:8, wherein the diameter of CNF is 35-58 nm, the length of CNF is 424-718 nm, the diameter of CNC is 15-20 nm, the length of CNF is 172-243 nm, and the addition amount of CNF/CNC is 8.0% of the total mixed slurry mass formed by CF/SF+CNF/CNC), so as to prepare the CF/SF/NF composite slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.15wt%, and performing wet hot pressing treatment for 30min at the temperature of 95 ℃ and the pressure of 18MPa to obtain the high-barrier cellulose-based paper packaging material.
The performance indexes of the high-barrier cellulose base paper packaging material prepared in the embodiment are as follows: quantification: 55g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 4.2kN/m; tear strength: 234.7mN; oxygen transmission rate: 2.4cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 135g/m 2 ·day。
Comparative example 1
The comparative example provides a preparation method of a cellulose base paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: pulping cotton fiber (with the length of 33-38 mm and the diameter of 7-14 μm) in a PFI mill, wherein the pulping revolution is 5000 revolutions, the pulping concentration is 2.0wt% and the pulping degree is 50 DEG SR; sisal fibers (length of 18-22 mm, diameter of 33-38 μm) were beaten in a PFI mill at 8000 revolutions, at 2.0wt% beaten concentration and at 40 ° SR. Then dispersing cotton fiber in an electric dispersing machine with the rotating speed of 4000r/min for 15min at the concentration of 1.5 mass percent; sisal fibers were dispersed at a concentration of 1.0% by mass in an electric disperser at 5000r/min for 10min. Finally, the cotton fiber dispersion liquid and the sisal fiber dispersion liquid after the dispersion treatment are subjected to absolute dry mass ratio of 4:5, uniformly mixing to obtain the CF/SF mixed slurry solution.
(2) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF compound slurry obtained in the step (1) on an inclined wire paper machine at the slurry concentration of 0.06wt%, and performing wet hot pressing treatment for 15min at the temperature of 80 ℃ and the pressure of 16MPa to obtain the cellulose base paper packaging material.
The performance indexes of the cellulose base paper wrapping material prepared in this comparative example are as follows: quantification: 65g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 1.5kN/m; tear strength: 176.4mN; oxygen transmission rate: 8.1cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 227g/m 2 ·day。
Comparative example 2
The comparative example provides a preparation method of a cellulose base paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: pulping cotton fiber (with the length of 33-38 mm and the diameter of 7-14 μm) in a PFI mill, wherein the pulping revolution is 5000 revolutions, the pulping concentration is 2.0wt% and the pulping degree is 50 DEG SR; sisal fibers (length of 18-22 mm, diameter of 33-38 μm) were beaten in a PFI mill at 8000 revolutions, at 2.0wt% beaten concentration and at 40 ° SR. Then dispersing cotton fiber in an electric dispersing machine with the rotating speed of 4000r/min for 15min at the concentration of 1.5 mass percent; sisal fibers were dispersed at a concentration of 1.0% by mass in an electric disperser at 5000r/min for 10min. Finally, the cotton fiber dispersion liquid and the sisal fiber dispersion liquid after the dispersion treatment are subjected to absolute dry mass ratio of 4:5, uniformly mixing to obtain the CF/SF mixed slurry solution.
(2) Wet end addition of nanocellulose: adding CNF suspension with mass concentration of 5.0% (CNF diameter 20-53 nm, length 335-672 nm, and CNF addition amount of 1.0% of the mass of the mixed slurry formed by CF/SF+CNF) into the CF/SF mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 4000 r/min) to prepare the CF/SF/CNF compound slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/CNF compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.06wt%, and performing wet hot pressing treatment for 15min at the temperature of 80 ℃ and the pressure of 16MPa to obtain the cellulose base paper packaging material.
The performance indexes of the cellulose base paper wrapping material prepared in this comparative example are as follows: quantification: 62g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 2.3kN/m; tear strength: 202.5mN; oxygen transmission rate: 6.4cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 183g/m 2 ·day。
Comparative example 3
The comparative example provides a preparation method of a cellulose base paper packaging material, which comprises the following specific preparation steps:
(1) Compounding fiber slurry: bagasse fibers (with the length of 0.6-3.3 mm and the diameter of 17-26 mu m, provided by key laboratories of pulping and papermaking engineering countries) are subjected to pulping treatment in a PFI mill, wherein the pulping revolution is 5000 revolutions, the pulping concentration is 2.0wt% and the pulping degree is 50 DEG SR; eucalyptus fibers (length of 0.8-1.7 mm, diameter of 15-24 μm, and provided by national key laboratory of pulping and papermaking engineering) were subjected to pulping treatment in a PFI mill, the number of pulping revolutions was 8000 revolutions, the pulping concentration was 2.0wt%, and the degree of pulping was 40 ° SR. Then dispersing bagasse fibers in an electric dispersing machine with the rotating speed of 4000r/min for 15min at the concentration of 1.5 mass percent; sisal fibers were dispersed at a concentration of 1.0% by mass in an electric disperser at 5000r/min for 10min. Finally, dispersing the bagasse fiber dispersion liquid and the eucalyptus fiber dispersion liquid which are subjected to dispersion treatment according to an absolute dry mass ratio of 4:5 (namely, the mass ratio of bagasse fibers in the bagasse fiber dispersion liquid to eucalyptus fibers in the eucalyptus fiber dispersion liquid) to obtain a bagasse fiber/eucalyptus fiber mixed slurry solution.
(2) Wet end addition of nanocellulose: adding a CNF/CNC suspension with the mass concentration of 5.0% into the bagasse fiber/eucalyptus fiber mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 4000 r/min) (the absolute dry mass ratio of CNF to CNC is 1:6, wherein the diameter of CNF is 20-53 nm, the length is 335-672 nm, the diameter of CNC is 12-17 nm, the length is 150-231 nm, and the addition amount of CNF/CNC is 1.0% of the mass of the mixed slurry formed by bagasse fiber/eucalyptus fiber+CNF/CNC), so as to prepare the compound slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.06wt%, and performing wet hot pressing treatment for 15min at the temperature of 80 ℃ and the pressure of 16MPa to obtain the cellulose base paper packaging material.
The performance indexes of the high-barrier cellulose base paper packaging material prepared in the comparative example are as follows: quantification: 58g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 1.7kN/m; tear strength: 187.5mN; oxygen transmission rate: 6.8cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 202g/m 2 ·day。
Comparative example 4
The comparative example provides a preparation method of a cellulose base paper packaging material, which comprises the following specific preparation steps:
(1) Compounding long fiber slurry: bagasse fibers (with the length of 0.6-3.3 mm and the diameter of 17-26 mu m, provided by key laboratories of pulping and papermaking engineering countries) are subjected to pulping treatment in a PFI mill, wherein the pulping revolution is 5000 revolutions, the pulping concentration is 2.0wt% and the pulping degree is 50 DEG SR; sisal fibers (length of 18-22 mm, diameter of 33-38 μm) were beaten in a PFI mill at 8000 revolutions, at 2.0wt% beaten concentration and at 40 ° SR. Then dispersing bagasse fibers in an electric dispersing machine with the rotating speed of 4000r/min for 15min at the concentration of 1.5 mass percent; sisal fibers were dispersed at a concentration of 1.0% by mass in an electric disperser at 5000r/min for 10min. Finally, dispersing the bagasse fiber dispersion liquid and sisal fiber dispersion liquid in a absolute dry mass ratio of 4:5 (i.e. the mass ratio of bagasse fibers in the bagasse fiber dispersion liquid to sisal fibers in the sisal fiber dispersion liquid) to obtain a bagasse fiber/sisal fiber mixed slurry solution.
(2) Wet end addition of nanocellulose: adding 5.0% of CNF/CNC suspension (the absolute dry mass ratio of CNF to CNC is 1:6, wherein the diameter of CNF is 20-53 nm, the length is 335-672 nm, the diameter of CNC is 12-17 nm, the length is 150-231 nm, and the addition amount of CNF/CNC is 1.0% of the mass of the mixed slurry formed by bagasse fiber/eucalyptus fiber+CNF/CNC) into the bagasse fiber/sisal hemp fiber mixed slurry solution in the step (1) under the condition of high-speed stirring (rotating speed: 4000 r/min), so as to prepare the compound slurry.
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the compound slurry obtained in the step (2) on an inclined wire paper machine at the slurry concentration of 0.06wt%, and performing wet hot pressing treatment for 15min at the temperature of 80 ℃ and the pressure of 16MPa to obtain the cellulose base paper packaging material.
The performance index of the high barrier cellulose-based paper wrapper of this comparative example is as follows: quantification: 60g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the Tensile strength: 2.3kN/m; tear strength: 197.4mN; oxygen transmission rate: 7.1cm 3 /m 2 Day 0.1MPa; water vapor transmission rate: 196g/m 2 ·day。
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-barrier cellulose-based paper packaging material is characterized by comprising the following steps of:
(1) Compounding long fiber slurry: pulping cotton fiber and sisal fiber respectively, then fully dispersing to obtain cotton fiber dispersion liquid and sisal fiber dispersion liquid, and uniformly mixing the cotton fiber dispersion liquid and the sisal fiber dispersion liquid to obtain CF/SF mixed slurry;
(2) Wet end addition of nanocellulose: adding plant-based nanocellulose into the CF/SF mixed slurry obtained in the step (1) under the stirring condition, and uniformly mixing to obtain CF/SF/NF compound slurry; wherein the plant-based nanocellulose is plant cellulose nanofibrils and plant cellulose nanocrystals;
(3) And (3) composite papermaking treatment: and (3) manufacturing and forming the CF/SF/NF compound slurry obtained in the step (2), and performing wet heat pressing treatment to obtain the high-barrier cellulose-based paper packaging material.
2. The method for preparing the high-barrier cellulose-based paper wrapper according to claim 1, wherein:
the mass ratio of the cotton fibers in the cotton fiber dispersion liquid to the sisal fibers in the sisal fiber dispersion liquid in the step (1) is 4-6: 5 to 7;
the concentration of the plant-based nanocellulose in the step (2) is 5.0-7.0% by mass;
the addition amount of the plant-based nanocellulose in the step (2) is 1.0-8.0% of the mass of the CF/SF/NF compound slurry;
the mass ratio of the plant cellulose nanofibrils to the plant cellulose nanocrystalline in the step (2) is 1-2: 6 to 8;
the concentration of the CF/SF/NF compound slurry in the step (3) is 0.06-0.15% by mass.
3. The method for preparing the high-barrier cellulose-based paper wrapper according to claim 1, wherein:
the length of the cotton fiber in the step (1) is 25-38 mm, and the diameter is 7-20 mu m; the length of the sisal fiber is 13-22 mm, and the diameter is 33-48 mu m;
the beating revolution of the cotton fiber in the step (1) is 5000-8000 revolutions, the beating concentration is 2.0-4.0%, and the beating degree is 50-70 DEG SR; the beating revolution of sisal fiber is 8000-10000 revolutions, the beating concentration is 2.0-3.0%, and the beating degree is 40-50 DEG SR;
dispersing cotton fibers in the dispersing treatment in the step (1) in an electric dispersing machine with the rotating speed of 4000-6000 r/min for 15-25 min at the concentration of 1.5-2.0% by mass percent; dispersing sisal fibers in an electric dispersing machine with the rotating speed of 5000-8000 r/min for 10-20 min at the concentration of 1.0-3.0% by mass percent;
the diameter of the plant cellulose nanofibrils in the step (2) is 20-60 nm, and the length is 300-800 nm;
the diameter of the plant cellulose nanocrystalline in the step (2) is 10-20 nm, and the length is 150-250 nm.
4. The method for producing a high-barrier cellulose-based paper wrapper according to claim 3, wherein:
the plant cellulose nanofibrils in the step (2) are prepared by taking softwood pulp as a raw material through mechanical grinding and high-pressure homogenization; wherein, the conditions of mechanical grinding are as follows: grinding 10 times under 0 and-50 μm gap, with rotation speed of 1200rpm; then the clearance of the grinding disc is adjusted to-100 mu m for grinding for 20 times, and the rotating speed is 1800rpm; the conditions of high-pressure homogenization are as follows: the temperature is 25 ℃, the operating pressure is 150MPa, and the cycle is 3 times;
the plant cellulose nanocrystalline in the step (2) is prepared from microcrystalline cellulose serving as a raw material through organic acid hydrolysis: adding microcrystalline cellulose into maleic acid solution, stirring for hydrolysis at 40+ -5deg.C, adding water to terminate acid hydrolysis reaction, centrifuging for washing, collecting lower layer solid, dialyzing, and collecting upper layer light blue solution for rotary evaporation concentration to obtain CNC suspension.
5. The method for preparing the high-barrier cellulose-based paper wrapper according to claim 1, wherein:
the wet and hot pressure conditions in the step (3) are as follows: the temperature is 80-95 ℃, the pressure is 16-18 MPa, and the time is 15-30 min.
6. The method for preparing the high-barrier cellulose-based paper wrapper according to claim 1, wherein:
the beating treatment in the step (1) adopts a PFI mill to carry out beating treatment;
the stirring rotating speed in the step (2) is 4000-6000 r/min;
and (3) the paper making and forming is carried out by adopting an inclined wire paper machine.
7. The utility model provides a high separation cellulose base paper package material which characterized in that: is prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the high barrier cellulose based paper wrapper of claim 7 in packaging materials.
9. The use according to claim 8, characterized in that: the packaging material comprises a packaging fresh-keeping material.
10. The use according to claim 9, characterized in that: the packaging material is a packaging fresh-keeping material for fresh and/or fruits.
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