CN117536012A - Bio-based barrier composition, preparation method thereof, composition for preparing pulp molded product and pulp molded product - Google Patents
Bio-based barrier composition, preparation method thereof, composition for preparing pulp molded product and pulp molded product Download PDFInfo
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- CN117536012A CN117536012A CN202310421471.9A CN202310421471A CN117536012A CN 117536012 A CN117536012 A CN 117536012A CN 202310421471 A CN202310421471 A CN 202310421471A CN 117536012 A CN117536012 A CN 117536012A
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- 230000004888 barrier function Effects 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 150000004676 glycans Chemical class 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 22
- 239000005017 polysaccharide Substances 0.000 claims abstract description 22
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 18
- 229920000229 biodegradable polyester Polymers 0.000 claims abstract description 17
- 239000004622 biodegradable polyester Substances 0.000 claims abstract description 17
- 239000001993 wax Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- 229920001661 Chitosan Polymers 0.000 claims description 16
- 230000005540 biological transmission Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 7
- 235000013539 calcium stearate Nutrition 0.000 claims description 7
- 239000008116 calcium stearate Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000007766 cera flava Substances 0.000 claims description 4
- 230000006196 deacetylation Effects 0.000 claims description 4
- 238000003381 deacetylation reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 4
- 229920000921 polyethylene adipate Polymers 0.000 claims description 4
- 241000238631 Hexapoda Species 0.000 claims description 3
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 239000004204 candelilla wax Substances 0.000 claims description 3
- 235000013868 candelilla wax Nutrition 0.000 claims description 3
- 229940073532 candelilla wax Drugs 0.000 claims description 3
- 239000004203 carnauba wax Substances 0.000 claims description 3
- 239000007765 cera alba Substances 0.000 claims description 3
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 3
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 3
- -1 polyethylene adipate Polymers 0.000 claims description 3
- 239000012180 soy wax Substances 0.000 claims description 3
- 229940045860 white wax Drugs 0.000 claims description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 24
- 230000007613 environmental effect Effects 0.000 abstract description 13
- 238000000465 moulding Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 229920001131 Pulp (paper) Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000013055 pulp slurry Substances 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 2
- 235000007201 Saccharum officinarum Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/25—Cellulose
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/53—Polyethers; Polyesters
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/60—Waxes
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/08—Dispersing agents for 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
Abstract
The application relates to a bio-based barrier composition and a preparation method thereof, a composition for preparing a pulp molded product and the pulp molded product, wherein the bio-based barrier composition comprises the following components in parts by weight: 100 parts of micro-nano cellulose; 12.5 to 40 parts of biological wax; 3.3 to 8 parts of biodegradable polysaccharide polymer; 8.3 to 25 parts of biodegradable polyester; 0.58 to 2.5 portions of compatilizer; 241-600 parts of dispersing agent; 391 to 650 portions of water. The bio-based barrier composition provided by the application can simplify the process of the pulp molding product with barrier property and improve the environmental protection property and the barrier property of the pulp molding product.
Description
Technical Field
The application relates to the technical field of pulp molded products, in particular to a bio-based barrier composition and a preparation method thereof, a composition for preparing the pulp molded products and the pulp molded products.
Background
The pulp molded product can contain packaged products, and reduce the probability of damage during transportation, loading and unloading and use. With the development of pulp molding manufacturing technology, performance improvement, such as barrier performance, can be performed according to the packaging requirements of different products, and the packaged products can be protected by better barrier performance, so that adverse effects of the penetration of external factors on the packaged products are reduced. In addition, the environmental performance of pulp molded articles is also a considerable improvement. Thus, there is a need to improve the barrier properties and environmental protection properties of pulp molded articles.
However, in the related art, the pulp molded article is subjected to a special process treatment to form a coating layer having barrier properties on the surface thereof, and the barrier auxiliary used for the coating layer may cause deterioration of environmental protection properties of the pulp molded article. In addition, the barrier properties of the pulp molded articles are still to be improved.
Disclosure of Invention
The application provides a bio-based barrier composition and a preparation method thereof, a composition for preparing a pulp molded product and the pulp molded product, which can simplify the process of the pulp molded product with barrier property and improve the environmental protection property and the barrier property of the pulp molded product.
In a first aspect, the present application provides a bio-based barrier composition comprising, in parts by weight:
100 parts of micro-nano cellulose;
12.5 to 40 parts of biological wax;
3.3 to 8 parts of biodegradable polysaccharide polymer;
8.3 to 25 parts of biodegradable polyester;
0.58 to 2.5 portions of compatilizer;
241-600 parts of dispersing agent;
391 to 650 portions of water.
In the bio-based barrier composition provided by the application, the components and the matching content are reasonably selected, so that the bio-based barrier composition has biodegradability and can be directly added into paper pulp for preparing paper pulp molded products, and the barrier performance of the paper pulp molded products is improved while the process of the paper pulp molded products with the barrier performance is simplified. Thus, the bio-based barrier composition provided by the application can simplify the process of providing a pulp molded product with barrier properties and improve the environmental protection performance and barrier properties of the pulp molded product.
According to any of the foregoing embodiments of the first aspect of the present application, the composition comprises:
100 parts of micro-nano cellulose;
30-33 parts of biological wax;
6-8 parts of biodegradable polysaccharide polymer;
20-25 parts of biodegradable polyester;
0.88 to 2.15 portions of compatilizer;
300-400 parts of dispersing agent;
600-650 parts of water.
According to any of the foregoing embodiments of the first aspect of the present application, the biodegradable polysaccharide polymer comprises chitosan;
and/or the weight average molecular weight of the chitosan is 20-50 ten thousand;
and/or, the deacetylation degree of chitosan is greater than or equal to 85%.
According to any of the foregoing embodiments of the first aspect of the present application, the biodegradable polyester comprises one or more of polyhydroxyalkanoate, poly 3-hydroxybutyrate, poly (3-hydroxybutyrate-3-hydroxyvalerate), polyhydroxybutyrate caproate, and polyethylene adipate.
According to any of the foregoing embodiments of the first aspect of the present application, the biological wax comprises one or more of white beeswax, yellow beeswax, insect white wax, palm wax, soy wax and candelilla wax.
According to any of the foregoing embodiments of the first aspect of the present application, the compatibilizing agent comprises a calcium salt;
optionally, the compatibilizing agent comprises one or more of calcium chloride and calcium stearate;
optionally, the compatilizer comprises 0.33 to 1 part of calcium chloride and 0.25 to 1.5 parts of calcium stearate based on 100 parts by weight of micro-nano cellulose.
According to any of the foregoing embodiments of the first aspect of the present application, the dispersant comprises one or more of glacial acetic acid and ethanol;
optionally, the dispersing agent comprises 158-300 parts of glacial acetic acid and 83-300 parts of ethanol based on 100 parts by weight of micro-nano cellulose.
In a second aspect, the present application provides a method of preparing a bio-based barrier composition as in the first aspect of the present application, comprising:
dispersing biological wax and partial compatilizer in a solvent and performing first water bath treatment to obtain biological wax dispersion liquid;
mixing the biological wax dispersion liquid and part of biodegradable polysaccharide polymer with part of dispersing agent, and performing second water bath treatment to obtain a first mixed solution;
mixing the biodegradable polyester with the rest of the biodegradable polysaccharide polymer, a compatilizer and a dispersing agent to obtain a second mixed solution;
and adding the first mixed solution and the second mixed solution into the solvent in which the micro-nano cellulose is dispersed, and performing mixing treatment to obtain the bio-based barrier composition.
In a third aspect, the present application provides a composition for making a pulp molded article comprising, based on 100% mass fraction of the composition for making a pulp molded article:
oven-drying pulp, 0.1% -3%;
92.5 to 97.5 percent of water;
0.15 to 4.5 percent of additive;
wherein the additive comprises the bio-based barrier composition of the first aspect of the application or the bio-based barrier composition prepared by the preparation method of the second aspect of the application.
In a fourth aspect, the present application provides a pulp molded article prepared using the composition of the third aspect of the present application for preparing a pulp molded article.
According to any of the foregoing embodiments of the fourth aspect of the present application, the pulp molded article has a water vapor transmission rate of 90% RH at 38℃per 100 μm thickness of less than or equal to 200g/m 2 ·day；
Alternatively, the pulp molded article has a water vapor transmission rate of 90% RH at 38℃per 100 μm thickness in the range of 120g/m 2 ·day～200g/m 2 ·day。
In a fifth aspect, the present application provides a method of making a pulp molded article as in the fourth aspect of the present application, comprising:
dispersing an additive containing a bio-based barrier composition and absolute dry paper pulp in water, heating and stirring to obtain paper pulp slurry;
pulp slurry is subjected to pulp suction, forming, hot pressing and drying treatment to obtain a pulp molding product.
Detailed Description
Where a composition is described as comprising or including a particular component, it is contemplated that optional components not referred to herein are not excluded from the composition, and that the composition may consist or consist of the recited components, or where a method is described as comprising or including a particular process step, it is contemplated that optional process steps not recited herein are not excluded from the method, and that the method may consist or consist of the recited process steps.
The terms "optional" and "optionally" refer to embodiments of the present application that may provide certain benefits in certain circumstances. However, other embodiments may be optional under the same or other circumstances. In addition, recitation of one or more alternative embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the application.
As used herein, "a," "an," "at least one," and "one or more" are used interchangeably. Thus, for example, a coating composition comprising "one" additional additive may be interpreted to mean that the coating composition comprises "one or more" additional additives.
For simplicity, some numerical ranges are disclosed herein, however, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In various examples, the list is merely a representative group and should not be construed as exhaustive.
As described in the background art above, pulp molded articles are capable of accommodating and protecting packaged products, and in order to obtain a good protection of the packaged products, pulp molded articles are generally formed with a barrier coating on the surface thereof, which is formed by spraying, knife coating, dipping, or the like. However, the barrier aids used in the barrier coating may lead to reduced environmental performance of the pulp molded article. In addition, the barrier properties of the pulp molded articles are still to be improved.
In the present application, the pulp molded product may be a color box, a gift box, a carton, a paper holder, an intelligent package, an environment-friendly package, a functional package, or the like, and the embodiment of the present application is not particularly limited herein.
Bio-based barrier composition
In a first aspect, the present application provides a bio-based barrier composition comprising, in parts by weight:
100 parts of micro-nano cellulose;
12.5 to 40 parts of biological wax;
3.3 to 8 parts of biodegradable polysaccharide polymer;
8.3 to 25 parts of biodegradable polyester;
0.58 to 2.5 portions of compatilizer;
241-600 parts of dispersing agent;
391 to 650 portions of water.
In the bio-based barrier composition provided by the application, the components and the matching content are reasonably selected, so that the bio-based barrier composition has biodegradability and can be directly added into paper pulp for preparing paper pulp molded products, and the barrier performance of the paper pulp molded products is improved while the process of the paper pulp molded products with the barrier performance is simplified. Thus, the bio-based barrier composition provided by the application can simplify the process of providing a pulp molded product with barrier properties and improve the environmental protection performance and barrier properties of the pulp molded product.
In some embodiments of the present application, the bio-based barrier composition comprises the following components:
100 parts of micro-nano cellulose;
30-33 parts of biological wax;
6-8 parts of biodegradable polysaccharide polymer;
20-25 parts of biodegradable polyester;
0.88 to 2.15 portions of compatilizer;
300-400 parts of dispersing agent;
600-650 parts of water.
In the present application, the biodegradable polysaccharide polymer can help to disperse the bio-wax and also to improve the stability of the bio-wax in the bio-based barrier composition to improve the barrier properties of the pulp molded article.
In some embodiments of the present application, the biodegradable polysaccharide polymer comprises one or more of chitosan, starch, and alginate. Wherein the chitosan has hydroxyl groups and amino groups, and the chitosan can further improve the dispersibility of the biological wax and the stability of the biological wax in the biological-based barrier composition.
In some embodiments of the present application, the weight average molecular weight of the chitosan is 20 to 50 tens of thousands, and when the weight average molecular weight of the chitosan is in the above-mentioned suitable range, it may contribute to the improvement of the dispersibility thereof and the bio-based barrier composition to the improvement of the barrier properties of pulp molded articles.
Exemplary weight average molecular weights of chitosan may be, but are not limited to, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or any two of the above ranges, for example, the weight average molecular weight range of chitosan may be, but is not limited to, 21 to 48, 25 to 45, 30 to 40.
In some embodiments of the present application, the chitosan has a degree of deacetylation greater than or equal to 85%.
In some embodiments of the present application, the biodegradable polyester comprises one or more of Polyhydroxyalkanoate (PHA), poly 3-hydroxybutyrate (PHB), poly (3-hydroxybutyrate-3-hydroxyvalerate) (PHBV), polyhydroxybutyrate caproate (PHBHHx), and polyethylene adipate (PEA).
In some embodiments of the present application, the biodegradable polyester comprises poly (3-hydroxybutyrate-3-hydroxyvalerate) (PHBV) that can help to improve the stability of the bio-wax in the bio-based barrier composition, but also can help the bio-based barrier composition to improve the environmental and barrier properties of pulp molded articles.
In some embodiments of the present application, the biological wax includes one or more of white beeswax, yellow beeswax, insect white wax, palm wax, soy wax, and candelilla wax.
In some embodiments of the present application, the compatibilizing agent comprises a calcium salt that can help increase the compatibility between the other components in the bio-based barrier composition to improve the uniformity of the components in the dispersion.
In some embodiments of the present application, the compatibilizing agent comprises one or more of calcium chloride and calcium stearate.
In some embodiments of the present application, the compatibilizer comprises 0.33 to 1 part of calcium chloride and 0.25 to 1.5 parts of calcium stearate based on 100 parts by weight of the micro-nanocellulose.
In some embodiments of the present application, the dispersant comprises one or more of glacial acetic acid and ethanol. Wherein, the ethanol can be absolute ethanol.
In some embodiments of the present application, the dispersant comprises 158 to 300 parts glacial acetic acid and 83 to 300 parts ethanol, based on 100 parts by weight of the micro-nano cellulose.
In some embodiments of the present application, the component water included in the bio-based barrier composition may be deionized water.
Preparation method of bio-based resistor composition
In a second aspect, the present application provides a method of preparing a bio-based barrier composition as in the first aspect of the present application, comprising:
s10, dispersing biological wax and part of compatilizer in a solvent and performing first water bath treatment to obtain biological wax dispersion liquid;
s20, mixing the biological wax dispersion liquid, part of biodegradable polysaccharide polymer and part of dispersing agent, and performing second water bath treatment to obtain a first mixed solution;
s30, mixing the biodegradable polyester with the rest of the biodegradable polysaccharide polymer, the compatilizer and the dispersing agent to obtain a second mixed solution;
and S40, adding the first mixed solution and the second mixed solution into the solvent in which the micro-nano cellulose is dispersed, and mixing the first mixed solution and the second mixed solution to obtain the bio-based barrier composition.
In the preparation method provided by the application, the compatibility among the components is good, a dispersion system with good uniformity can be obtained, and the prepared bio-based barrier composition can be mixed with paper pulp to prepare a paper pulp molding product, so that the process of the paper pulp molding product with barrier property is simplified, and the environmental protection property and the barrier property of the paper pulp molding product are improved.
In some embodiments of the present application, the bio-wax, a portion of the compatibilizer, are dispersed in a solvent and subjected to a first water bath treatment to obtain a bio-wax dispersion, i.e., S10 includes:
s11, dispersing biological wax and part of compatilizer in a solvent and performing first ultrasonic water bath treatment to obtain biological wax dispersion liquid; wherein the ultrasonic power is 40W-100W, and the ultrasonic time is 30 min-60 min. The above-described ultrasonic water bath treatment may aid in the dispersion of the biological wax.
In some embodiments of the present application, the bio-wax dispersion, a portion of the biodegradable polysaccharide polymer, and a portion of the dispersant are mixed and subjected to a second ultrasonic water bath to obtain a first mixed solution, i.e., S20 comprises:
s21, mixing the biological wax dispersion liquid, part of biodegradable polysaccharide polymer and part of dispersing agent, and performing second ultrasonic water bath treatment to obtain a first mixed solution, wherein the ultrasonic power is 40-100W, and the ultrasonic time is 30-60 min
In some embodiments of the present application, the biodegradable polysaccharide polymers used in S20 and S30 have a weight average molecular weight of 20 to 50 tens of thousands and a degree of deacetylation of 85% or more.
In some embodiments of the present application, the biodegradable polyester used in S30 comprises PHBV, which can help to improve the stability of the bio-wax in the bio-based barrier composition, but also can help the bio-based barrier composition to improve the environmental and barrier properties of the pulp molded article.
In these examples, PHBV may be in powder form, and have a fineness of 150 meshes or more, a viscosity average molecular weight of 40 tens of thousands or more, and a relative density of 1.22 to 1.25.
In some embodiments of the present application, the biodegradable polyester is mixed with the remaining portion of the biodegradable polysaccharide polymer, the compatibilizer, and the dispersant to obtain a second mixed solution, i.e., S30 includes:
the biodegradable polyester is mixed with the rest of the biodegradable polysaccharide polymer, the compatilizer and the dispersing agent, and then is placed in a cell pulverizer to be dispersed, so as to obtain a second mixed solution.
In these examples, the cell disruptor power was 300W to 650W and the treatment time was 30min to 60min.
In some embodiments of the present application, the micro-nanocellulose employed in S40 may be an aqueous dispersion, with a solids content of 10% ± 3%.
Composition for preparing pulp molded articles
In a third aspect, the present application provides a composition for making a pulp molded article comprising, based on 100% mass fraction of the composition for making a pulp molded article:
oven-drying pulp, 0.1% -3%;
92.5 to 97.5 percent of water;
0.15 to 4.5 percent of additive;
wherein the additive comprises the bio-based barrier composition of the first aspect of the application or the bio-based barrier composition prepared by the preparation method of the second aspect of the application.
In the composition for preparing the pulp molded product, provided by the application, the biological-based barrier composition in the embodiment can simplify the process of preparing the pulp molded product with barrier property and improve the environmental protection property and the barrier property of the pulp molded product.
In this application, the oven-dried pulp may be selected according to practical application requirements, and exemplary oven-dried pulp includes one or more of bamboo pulp, sugarcane pulp, wood pulp, straw pulp, and waste pulp.
Pulp molded article
In a fourth aspect, the present application provides a pulp molded article prepared using the composition of the third aspect of the present application for preparing a pulp molded article.
In some embodiments of the present application, the pulp molded article has a water vapor transmission rate of less than or equal to 200g/m at 38℃and 90% RH per 100 μm thickness 2 Day. The pulp molded product has proper water vapor transmission rate range under the above conditions, and can have better barrier property.
In this application, the amount of water vapor transmission has the meaning well known in the art and can be tested using instrumentation or methods well known in the art. For example, the test is carried out by using a water vapor transmission rate tester according to the weight reduction method in the national standard "GB/T1037-2021 plastic film and flake water vapor transmission performance measuring cup type weight gain and weight reduction method", and comprises the following steps:
distilled water is added into the dry and clean moisture permeable cup, the sample is packaged on the moisture permeable cup, the moisture permeable cup is placed in the test cavity in a state that the cup opening is upward, and the cavity door is closed. 38℃and 90% RH were set up through the software interface and the test was started, yielding a water vapor transmission rate.
In some embodiments of the present application, the pulp molded article has a water vapor transmission rate of about 38deg.C, 90% RH per 100 μm thickness in the range of 120g/m 2 ·day～200g/m 2 ·day。
In addition, pulp molded articles can also be tested for barrier properties by hot oil testing and hot water testing. Illustratively, the test is conducted according to the heat resistant oil test method in the national standard "GB/T36787-2018 pulp molded tableware", comprising the steps of:
placing the sample on a dry glass plate or a flat plate lined with filter paper, filling edible oil at 95+/-5 ℃, standing for 30min, observing whether the sample is deformed or not, and observing whether oil marks oozed out of the filter paper exist or not.
The hot water resistance test can be carried out according to the hot water resistance test method in national standard GB/T36787-2018 pulp molded tableware, and comprises the following steps:
placing the sample on a dry glass plate or a flat plate lined with filter paper, filling water at 95+/-5 ℃, standing for 30min, and observing whether the sample is deformed or not, and whether the bottom is oozed or leaked or not.
The present application provides a method of manufacturing a pulp molded article as in the fourth aspect of the present application, comprising:
dispersing an additive containing a bio-based barrier composition and absolute dry paper pulp in water, heating and stirring to obtain paper pulp slurry;
pulp slurry is subjected to pulp suction, forming, hot pressing and drying treatment to obtain a pulp molding product.
Examples
The following examples more particularly describe the disclosure of the present application, which are intended as illustrative only, since numerous modifications and variations within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available and can be used directly without further processing.
Test part
(1) Water vapor transmission capacity test
The water vapor permeability tester is used for testing according to the weight reduction method in the national standard GB/T1037-2021 plastic film and flake water vapor permeability test cup type weight increase and weight reduction method, and comprises the following steps:
distilled water is added into the dry and clean moisture permeable cup, the sample is packaged on the moisture permeable cup, the moisture permeable cup is placed in the test cavity in a state that the cup opening is upward, and the cavity door is closed. 38℃and 90% RH were set up through the software interface and the test was started, yielding a water vapor transmission rate.
Example 1
Preparation of biobased Barrier compositions
30 parts of yellow beeswax and 0.68 part of calcium chloride are dispersed in 200 parts of water and subjected to a first ultrasonic water bath treatment to obtain a biological wax dispersion, wherein the temperature of the first ultrasonic water bath is 85 ℃, the water bath time is 60min, and the ultrasonic power is 100W.
Mixing the biological wax dispersion liquid, 3 parts of chitosan and 90 parts of glacial acetic acid, and performing second ultrasonic water bath treatment to obtain a first mixed solution, wherein the second ultrasonic water bath temperature is 75 ℃, the water bath time is 60min, and the ultrasonic power is 100W.
Mixing 20 parts of PHBV, 5 parts of chitosan, 210 parts of glacial acetic acid, 1.25 parts of calcium stearate and 100 parts of absolute ethyl alcohol, and then placing the mixture in a cell pulverizer for dispersion to obtain a second mixed solution; the cell grinder power was 650W and the treatment time was 60min.
And adding the first mixed solution and the second mixed solution into 360 parts of water in which 100 parts of micro-nano cellulose is dispersed, and mixing to obtain the bio-based barrier composition.
Preparation of pulp molded articles
20 parts of straw pulp, 40 parts of bamboo pulp and 40 parts of sugarcane pulp are fluffed into pulp dispersion liquid with the concentration of 10%, 140 parts of biological base barrier composition are added and stirred uniformly, and water is added to dilute into mixed pulp with the concentration of 0.3% (calculated by absolute dry pulp). And (3) conveying the mixed slurry to a molding machine, carrying out vacuum filtration and dehydration to obtain a pulp molding product wet blank, and carrying out dehydration, hot-press shaping, transferring and trimming on the pulp molding product wet blank to obtain the pulp molding product.
Examples 2 to 10
Similar to the preparation of example 1, the difference is that: the components and amounts of the bio-based barrier composition.
Comparative examples 1 to 2
Similar to the preparation of example 1, the difference is that: the components and amounts of the bio-based barrier composition.
Table 1 lists the components and amounts thereof of the bio-based barrier compositions and the components and amounts thereof of the pulp molded articles and the related test results, respectively, in each of the examples and comparative examples.
From table 1, comparing the test results of examples 1 to 10 and comparative examples 1 to 2, it is apparent that the bio-based barrier composition can be directly added to pulp to prepare pulp molded articles while having biodegradability by reasonably selecting components and matching contents, thereby simplifying the process of pulp molded articles having barrier properties and improving the barrier properties of pulp molded articles. Thus, the bio-based barrier composition provided by the application can simplify the process of providing a pulp molded product with barrier properties and improve the environmental protection performance and barrier properties of the pulp molded product.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the embodiments, and are intended to be included within the scope of the claims and description. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.
Claims (11)
1. The bio-based barrier composition is characterized by comprising the following components in parts by weight:
100 parts of micro-nano cellulose;
12.5 to 40 parts of biological wax;
3.3 to 8 parts of biodegradable polysaccharide polymer;
8.3 to 25 parts of biodegradable polyester;
0.58 to 2.5 portions of compatilizer;
241-600 parts of dispersing agent;
391 to 650 portions of water.
2. The biobased barrier composition of claim 1, comprising the following components:
100 parts of micro-nano cellulose;
30-33 parts of biological wax;
6-8 parts of biodegradable polysaccharide polymer;
20-25 parts of biodegradable polyester;
0.88 to 2.15 portions of compatilizer;
300-400 parts of dispersing agent;
600-650 parts of water.
3. The bio-based barrier composition of claim 1 wherein the biodegradable polysaccharide polymer comprises chitosan;
and/or the weight average molecular weight of the chitosan is 20-50 ten thousand;
and/or, the deacetylation degree of the chitosan is greater than or equal to 85%.
4. The biobased barrier composition of claim 1, wherein the biodegradable polyester comprises one or more of polyhydroxyalkanoate, poly 3-hydroxybutyrate, poly (3-hydroxybutyrate-3-hydroxyvalerate), polyhydroxybutyrate caproate, and polyethylene adipate.
5. The bio-based barrier composition of claim 1 wherein the bio-wax comprises one or more of white beeswax, yellow beeswax, insect white wax, palm wax, soy wax and candelilla wax.
6. The bio-based barrier composition of claim 1 wherein the compatibiliser comprises a calcium salt;
optionally, the compatibilizing agent comprises one or more of calcium chloride and calcium stearate;
optionally, the compatilizer comprises 0.33 to 1 part of calcium chloride and 0.25 to 1.5 parts of calcium stearate based on 100 parts by weight of the micro-nano cellulose.
7. The bio-based barrier composition of claim 1 wherein the dispersant comprises one or more of glacial acetic acid and ethanol;
optionally, the dispersing agent comprises 158-300 parts of glacial acetic acid and 83-300 parts of ethanol based on 100 parts by weight of the micro-nano cellulose.
8. A process for preparing a bio-based barrier composition according to any one of claims 1 to 7, comprising:
dispersing biological wax and partial compatilizer in a solvent and performing first water bath treatment to obtain biological wax dispersion liquid;
mixing the biological wax dispersion liquid, part of biodegradable polysaccharide polymer and part of dispersing agent, and performing second water bath treatment to obtain a first mixed solution;
mixing the biodegradable polyester with the rest of the biodegradable polysaccharide polymer, a compatilizer and a dispersing agent to obtain a second mixed solution;
and adding the first mixed solution and the second mixed solution into the solvent in which the micro-nano cellulose is dispersed, and carrying out mixing treatment to obtain the bio-based barrier composition.
9. A composition for the preparation of pulp molded articles, characterized in that it comprises, calculated as 100% of the mass fraction of the composition for the preparation of pulp molded articles:
oven-drying pulp, 0.1% -3%;
92.5 to 97.5 percent of water;
0.15 to 4.5 percent of additive;
wherein the additive comprises the bio-based barrier composition of any one of claims 1 to 7 or the bio-based barrier composition prepared by the preparation method of claim 8.
10. A pulp molded article, characterized by being produced using the composition for producing a pulp molded article as defined in claim 9.
11. The pulp molded article according to claim 10, characterized in that the pulp molded article has a water vapor transmission rate of less than or equal to 200g/m at 38 ℃ at 90% rh per 100 μm thickness 2 ·day；
Alternatively, the pulp molded article has a water vapor transmission rate of 38 ℃ and 90% RH per 100 μm thickness ranging from 120g/m 2 ·day～200g/m 2 ·day。
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