CN116590956A - Hydrophobic-antibacterial pulp molding material, and preparation method and application thereof - Google Patents
Hydrophobic-antibacterial pulp molding material, and preparation method and application thereof Download PDFInfo
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- CN116590956A CN116590956A CN202310431558.4A CN202310431558A CN116590956A CN 116590956 A CN116590956 A CN 116590956A CN 202310431558 A CN202310431558 A CN 202310431558A CN 116590956 A CN116590956 A CN 116590956A
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- pulp
- chitin
- molding material
- pulp molding
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- 239000012778 molding material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002101 Chitin Polymers 0.000 claims abstract description 117
- 239000000835 fiber Substances 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
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- 125000002091 cationic group Chemical group 0.000 claims description 9
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- 238000004806 packaging method and process Methods 0.000 claims description 8
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- 241000609240 Ambelania acida Species 0.000 claims description 7
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- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
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- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 241001330002 Bambuseae Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 230000000850 deacetylating effect Effects 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000013051 drainage agent Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 239000002655 kraft paper Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 33
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
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- 238000005303 weighing Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 239000010893 paper waste Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000003381 deacetylation reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000743799 Calamagrostis Species 0.000 description 1
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- 241000195493 Cryptophyta Species 0.000 description 1
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- 241000238631 Hexapoda Species 0.000 description 1
- 241000237852 Mollusca Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/50—Spraying or projecting
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
-
- 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J3/00—Manufacture of articles by pressing wet fibre pulp, or papier-mâché, between moulds
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Paper (AREA)
Abstract
The invention belongs to the technical field of pulp molding, and discloses a hydrophobic-antibacterial pulp molding material, a preparation method and application thereof. The hydrophobic-antibacterial pulp molding material comprises a pulp molding material and a nano chitin coating coated on the pulp molding material. The paper pulp molding material with the nano chitin coating provided by the invention adopts paper pulp fibers and chitin as raw materials, and has the advantages of wide sources, easiness in degradation, environmental friendliness and the like; the preparation method is simple, the technological process is easy to control, the pollution generated in the production process is less, and the production cost is lower; the obtained hydrophobic-antibacterial pulp molding material has excellent hydrophobicity and antibacterial property, so that the application range of the nano chitin is widened, and more choices are provided for the application of the pulp molding material.
Description
Technical Field
The invention belongs to the technical field of pulp molding, and particularly relates to a hydrophobic-antibacterial pulp molding material, and a preparation method and application thereof.
Background
Chitin is widely distributed in nature and mainly exists in the shells of crustaceans, insect epidermis, mollusk endoskeleton, cell walls of algae and other microorganisms. Chitin is also called chitin and chitin, and is linear high polymer polysaccharide connected by beta-1, 4 glycosidic bond. Chitin has various excellent properties, such as good film forming property, flocculation, no toxicity, no irritation and the like, and has wide application in the industries of chemical industry, food, cosmetics and the like. However, the chitin has poor solubility in water and organic solvents, which greatly limits the application of the chitin in various fields.
The pulp molding material is prepared from primary fiber or secondary fiber, and the fiber can be from renewable resources such as waste paper, bagasse, wood, reed grass, reed and the like. Compared with the traditional plastic packaging material, the pulp molding material has lower raw material cost and is more environment-friendly. The preparation process of the pulp molding material mainly comprises the steps of pulp preparation, molding, drying, processing and the like. The material has the advantages of low cost of raw materials, easy acquisition, no pollution in the production process and the like. The pulp molding material has good properties of shock resistance, buffering, ventilation, static resistance and the like, so that the pulp molding material is widely applied in the fields of packaging and transportation. For example, pulp molding materials can be used for packaging fragile products such as electronic products, ceramics, glass, and the like. In addition, it can be used in the fields of food packaging, medical packaging, tableware and the like. The pulp molding material has wide application prospect, is particularly in the field of environment-friendly packaging, is hopeful to replace the traditional plastic packaging material, and becomes a more environment-friendly and sustainable material. However, disadvantages of this material include the relatively low strength and stability of the product, and the pulp molded product is generally not resistant to high temperatures, corrosion, water resistance, etc., and the range of applications is relatively limited.
1. The pulp molding material has poor water resistance and moisture resistance.
The pulp molding material is mainly prepared from plant fibers and has good hydrophilicity, so that the fiber structure is easy to absorb water and wet in contact with water or in a humid environment, and further the physical properties of the pulp molding material are greatly reduced, and the service life of pulp molding is seriously influenced. In order to solve the problems of insufficient hydrophilicity and physical strength of the existing pulp molding material, acrylic acid, polyethylene coating and the like are sprayed on the surface of the pulp molding material in the pulp molding and drying process to improve the water resistance of the pulp molding material, and in addition, the nano fiber with high length-diameter ratio can be used as reinforcing filler to be added into the pulp molding material to obviously improve the physical performance of the pulp molding material. For example, chinese patent publication CN106948224B discloses a method for producing a pulp molded article, in which an acrylic emulsion, distilled water, ethanol, a polyethylene wax emulsion, ammonia water, sodium dodecyl sulfate, etc. are mixed to prepare a spray solution, and the spray solution is uniformly coated on the surface of a pulp molded article dry blank, and dried. Although the method effectively improves the waterproof performance of the pulp molding product, spraying increases the surface treatment cost, and the coating is not degradable, thereby causing environmental pollution.
2. Poor antibacterial property
The pulp molding material is inevitably exposed to the water and oxygen conditions during the use process, bacteria are easy to grow on the surface of pulp fibers after long-term use, so that the use safety of the pulp molding material is not only bad, and challenges are presented to the sanitary health safety of goods supported in the pulp molding material, so that the use of some means for endowing the pulp molding material with the antibacterial property is very necessary.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks and deficiencies of the prior art, a primary object of the present invention is to provide a hydrophobic-antimicrobial pulp molding material.
It is another object of the present invention to provide a method for producing the above-mentioned hydrophobic-antibacterial pulp molding material.
According to the preparation method provided by the invention, the structure of the chitin is very similar to that of cellulose, the surface of the chitin is positively charged, the characteristics of nano cellulose are combined, the nano cellulose is favorably combined with pulp fibers, the film formation on the surface of a pulp molding material is favorably realized, and meanwhile, the hydrophobicity and the antibacterial property are endowed.
The nano chitin coated paper pulp molding material prepared by the invention has greatly improved hydrophobicity and antibacterial property.
It is still another object of the present invention to provide the use of the above-mentioned hydrophobic-antibacterial pulp molding material in the field of food and daily chemicals packaging.
The aim of the invention is achieved by the following scheme:
a hydrophobic-antibacterial pulp moulding material comprises a pulp moulding material and a nano chitin coating coated on the pulp moulding material.
The preparation of the hydrophobic-antibacterial pulp molding material comprises the following steps:
firstly, adding filler into pulp fiber suspension, uniformly mixing, and carrying out mould forming and hot-press drying to obtain a pulp molding material; purifying and pre-treating chitin, deacetylating, homogenizing to obtain nanometer chitin dispersion; finally, spraying the obtained nano chitin dispersion liquid on the surface of the pulp molding material, and carrying out hot pressing and drying to obtain the hydrophobic-antibacterial pulp molding material.
The preparation of the hydrophobic-antibacterial pulp molding material comprises the following steps:
(1) Adding retention and drainage aids and reinforcing agents into pulp fiber suspension, and adopting a rapid paper sheet forming technology to obtain a pulp molding material through mold forming and hot press drying;
(2) Sequentially soaking, filtering and washing chitin in sodium hydroxide, hydrochloric acid and sodium hypochlorite solution, and finally drying to obtain bleached chitin;
(3) Adding the bleached chitin in the step (2) into a mixed solution of sodium borohydride and sodium hydroxide, heating, stirring, filtering and washing to obtain deacetylated chitin;
(4) Dispersing the deacetylated chitin prepared in the step (3) in water, adding acid to adjust pH, and homogenizing to obtain nano chitin dispersion;
(5) And (3) spraying the nano chitin dispersion liquid prepared in the step (4) to form a uniform coating on the surface of the pulp molding material, and performing hot pressing and drying to obtain the hydrophobic-antibacterial pulp molding material.
The source of pulp fibers in step (1) comprises at least one of bleached chemical pulp, unbleached chemical pulp, chemimechanical pulp, waste pulp; preferably at least one of waste pulp, bleached/unbleached kraft pulp, bleached/unbleached bagasse pulp, bleached/unbleached bamboo pulp, bleached/unbleached straw pulp, bleached/unbleached chemimechanical pulp.
The retention and drainage agent in the step (1) is at least one of polyacetyl imine, polyamine, polyurethane and polyacrylamide, and the reinforcing agent is at least one of polyamide epichlorohydrin resin, melamine formaldehyde resin, urea formaldehyde resin, polyvinyl alcohol, carboxymethyl cellulose and cationic starch.
The mass of the retention and drainage aid in the step (1) is 0.01% -5% of the absolute dry mass of the pulp fibers; the mass of the reinforcing agent is 0.5-10% of the absolute dry mass of the pulp fiber.
The pulp fiber in the pulp molding material in the step (1) has the ration of 250-900 g/m 2 It means that 250-900 g pulp fiber is contained in each square meter of pulp molding material.
The chitin in the step (2) is crushed chitin, and the particle size after crushing is 100-500 mu m;
the mass concentration of the sodium hydroxide solution in the step (2) is 2% -8%; the soaking time is 1-5h; the mass ratio of the chitin to the sodium hydroxide solution is 1:10-20.
The mass concentration of the hydrochloric acid solution in the step (2) is 2% -8%; the soaking time is 1-5h; the mass ratio of the chitin to the hydrochloric acid solution is 1:10-20.
The mass concentration of the sodium hypochlorite solution in the step (2) is 0.2% -0.8%; the soaking time is 1-5h; the mass ratio of the chitin to the sodium hypochlorite solution is 1:10-20.
And (2) washing, namely washing the soaked chitin until the filtrate is neutral.
The temperature of the drying in the step (2) is 50-100 ℃.
The mass concentration of sodium hydroxide in the mixed solution in the step (3) is 32% -38%; the mass ratio of the bleached chitin to the sodium borohydride is 1:0.02-0.06; the mass ratio of the bleached chitin to the sodium hydroxide is 1:10-50.
The stirring speed in the step (3) is 100-600rpm, the heating temperature is 60-100 ℃, and the heating time is 1-5h.
The water dosage in the step (4) is as follows: so that the mass concentration of the nano chitin in the nano chitin dispersion liquid is 0.2-3%
The acid in the step (4) is one of hydrochloric acid, formic acid and acetic acid; the pH value is adjusted to 3.5-4.
The conditions of the homogenization treatment in the step (4) are as follows: the homogenizing pressure is 500bar-1100bar, and the homogenizing times are 10 times-100 times.
The dosage of the nano chitin dispersion liquid in the step (5) is as follows: the mass of the nano chitin is 0.1-20% of the absolute dry mass of the pulp fiber; preferably 0.5% -10%.
The application of the hydrophobic-antibacterial pulp molding material in the field of food and daily chemicals packaging.
The mechanism of the invention:
the nano chitin takes chitin as raw material, and through the pretreatment stage of the early solution, including sodium hydroxide, hydrochloric acid and sodium hypochlorite, protein, calcium carbonate impurities and the like in the chitin raw material are removed, so that the purity of the chitin is improved. Then deacetylating chitin, and homogenizing under acidic condition to obtain nano chitin; pulp fibers and various fillers are prepared into pulp molding material suspension according to a certain proportion, and the pulp molding material is obtained through mold forming and hot press drying; spraying the obtained nano chitin on the surface of a paper pulp molding material, and then carrying out hot-pressing drying treatment to obtain a finished product.
Compared with the prior art, the invention has the following advantages:
(1) The paper pulp molding material with the nano chitin coating provided by the invention adopts the nano chitin as the raw material, has rich sources, belongs to biomass raw materials capable of sustainable development, and has the advantages of safety, no toxicity, good biocompatibility, easiness in degradation, environmental friendliness and the like.
(2) The preparation method of the paper pulp molding material with the nano chitin coating has the advantages of simple production process, no need of cationization modification, simplified process, saved use amount of other chemicals and reduced production cost.
(3) According to the preparation method of the pulp molding material with the nano chitin coating, the raw material nano chitin used in the preparation method has the characteristics of chitin and the advantages of nano materials, so that the pulp molding material is endowed with excellent hydrophobicity and antibacterial property.
(4) The paper pulp molding material of the nano chitin coating expands the application range of nano chitin and provides more choices for the application of the paper pulp molding material.
Drawings
FIG. 1 is a schematic flow chart of the present invention.
Fig. 2 is an atomic force microscope image of nano-chitin prepared in the steps (2) - (3) of example 1.
FIG. 3 is a pulp molding microscopic surface (100 μm scale) of the uncoated nano-chitin prepared in comparative example 1.
FIG. 4 is a paper pulp molding microscopic surface (100 μm scale) coated with nano-chitin prepared in example 4.
Fig. 5 is a water contact angle of pulp molding of uncoated nano-chitin prepared in comparative example 1.
Fig. 6 is a water contact angle of the nano-chitin coated pulp molding prepared in example 4.
FIG. 7 is a graph showing the comparison of the antibacterial effect of example 4 and comparative example 1 (using the zone of inhibition method).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Polyacrylamide: purchased from An Naiji, having an average molecular weight of 6000000; cationic starch: purchased from An Naiji; chitin: purchased from An Naiji
Example 1
A pulp molding material with a hydrophobic coating and a preparation method thereof comprise the following steps:
(1) Weighing bleached bagasse pulp with an absolute dry mass of 15g, fully fluffing in a fluffer to obtain pulp fiber suspension, weighing high molecular weight polyacrylamide (with a molecular weight of 6000000) of a retention and drainage aid of 0.5g, adding 1g of cationic starch as an enhancer into the pulp suspension, stirring and mixing, and then performing die forming and hot press drying by using a rapid paper sheet forming technology to obtain the fiber suspension with a quantitative of 450g/m 2 Is a pulp molding material;
(2) Weighing 10g of crushed chitin with the grain diameter of 200 mu m, soaking the chitin into 200g of sodium hydroxide solution with the mass fraction of 5% for 1h, filtering, washing alkali liquor with distilled water, and washing until the filtrate is neutral; then soaking the chitin subjected to alkali treatment into 200mL of dilute hydrochloric acid solution with the mass fraction of 5% for 1h, and repeating the washing step of alkali treatment to obtain chitin subjected to acid treatment; soaking the chitin subjected to acid treatment in 150g of sodium hypochlorite solution with the mass fraction of 0.3% for bleaching for 1h, filtering, washing until the filtrate is neutral, and drying in an oven at 80 ℃ to obtain bleached chitin;
(3) And (3) performing deacetylation reaction on the bleached chitin in the step (2), firstly preparing 400g of 36% sodium hydroxide solution by mass fraction, adding 0.24g of sodium borohydride into the sodium hydroxide solution, uniformly mixing to obtain a mixed solution, adding 8g of the bleached chitin into the mixed solution, performing deacetylation reaction in a constant-temperature water bath at 90 ℃, continuously magnetically stirring, wherein the magnetic stirring revolution is 500 rpm, the reaction time is 2h, filtering, and washing the chitin with a large amount of distilled water to obtain the deacetylated chitin. And adding deionized water for dilution to ensure that the total volume of the suspension is 300mL, adjusting the pH of the suspension to 3.5 by using acetic acid, and homogenizing in a high-pressure homogenizer at 800bar for 20 times. Obtaining uniform nano chitin dispersion liquid, wherein the mass concentration of the nano chitin is 1.2%;
(4) The nano chitin dispersion liquid is evenly coated on the surface of the pulp molding material in a spraying mode, wherein the mass of the sprayed nano chitin dispersion liquid is 6.25g (the mass of the nano chitin is equivalent to 0.5 percent of the absolute dry mass of pulp fibers). And then completely drying the nano chitin coating on the pulp molding surface by using a hot press drying technology again, thus obtaining the pulp molding material with the nano chitin coating.
As shown in FIG. 2, the nano chitin prepared in example 1 has a size of 200-400nm, reaching the nano-scale.
Example 2
This example is identical to example 1 except for the following features, with the following differences:
and (4) uniformly coating the nano chitin dispersion liquid on the surface of the pulp molding material in a spraying manner, wherein the mass of the sprayed nano chitin dispersion liquid is 10g (the mass of the nano chitin is equivalent to 0.8% of the absolute dry mass of the pulp fiber). And then the hot press drying technology is used again to completely dry the nano chitin coating on the pulp molding surface, so that the pulp molding material with the nano chitin coating can be obtained.
Example 3
This example is identical to example 1 except for the following features, with the following differences:
and (4) uniformly coating the nano chitin dispersion liquid on the surface of the pulp molding material in a spraying manner, wherein the mass of the sprayed nano chitin dispersion liquid is 12.5g (the mass of the nano chitin is 1% of the absolute dry mass of the pulp fiber). And then the hot press drying technology is used again to completely dry the nano chitin coating on the pulp molding surface, so that the pulp molding material with the nano chitin coating can be obtained.
Example 4
This example is identical to example 1 except for the following features, with the following differences:
and (4) uniformly coating the nano chitin dispersion liquid on the surface of the pulp molding material in a spraying manner, wherein the mass of the sprayed nano chitin dispersion liquid is 25g (the mass of the nano chitin is 2% of the absolute dry mass of the pulp fiber). And then the hot press drying technology is used again to completely dry the nano chitin coating on the pulp molding surface, so that the pulp molding material with the nano chitin coating can be obtained.
Example 5
This example is identical to example 1 except for the following features, with the following differences:
weighing bleached bagasse pulp and waste paper pulp according to the weight ratio of 1:1, weighing total absolute dry mass of 15g, fully fluffing in a fluffer to obtain pulp fiber suspension, weighing high molecular weight polyacrylamide (molecular weight 6000000) of retention and drainage aid of 0.5g, adding 1g of cationic starch as reinforcing agent into the pulp suspension, stirring and mixing, molding by using a rapid paper sheet molding technology, and hot press drying to obtain the product with a weight of 450g/m 2 Is a pulp molding material of (a).
Example 6
This example is identical to example 1 except for the following features, with the following differences:
weighing unbleached bagasse pulp and waste paper pulp according to the weight ratio of 1:1, weighing total absolute dry mass of 15g, fully fluffing in a fluffer to obtain pulp fiber suspension, weighing high molecular weight polyacrylamide (molecular weight 6000000) of retention and drainage aid of 0.5g, adding 1g of cationic starch as reinforcing agent into the pulp suspension, stirring and mixing, molding by using a rapid paper sheet molding technology, and hot press drying to obtain the product with a weight of 450g/m 2 Is a pulp molding material of (a).
Example 7
This example is identical to example 1 except for the following features, with the following differences:
weighing bleached bamboo pulp and waste paper pulp according to the weight ratio of 1:1, weighing total absolute dry mass of 15g, fully fluffing in a fluffer to obtain pulp fiber suspension, weighing high molecular weight polyacrylamide (molecular weight 6000000) of retention and drainage aid 0.5g, adding 1g of cationic starch as reinforcing agentIn pulp suspension, stirring and mixing, and molding with a rapid paper sheet molding technique, and hot press drying to obtain a quantitative 450g/m 2 Is a pulp molding material of (a).
Example 8
This example is identical to example 1 except for the following features, with the following differences:
weighing unbleached chemimechanical wood pulp and waste paper pulp according to the weight ratio of 1:1, weighing total absolute dry mass of 15g, fully fluffing in a fluffer to obtain pulp fiber suspension, weighing high molecular weight polyacrylamide (molecular weight 6000000) of retention and drainage aid of 0.5g, adding 1g of cationic starch as reinforcing agent into the pulp suspension, stirring and mixing, molding by using a rapid paper sheet molding technology, and hot press drying to obtain the product with a weight of 450g/m 2 Is a pulp molding material of (a).
Comparative example 1
Weighing bleached bagasse pulp with an absolute dry mass of 15g, fully fluffing in a fluffer to obtain pulp fiber suspension, weighing high molecular weight polyacrylamide (with a molecular weight of 6000000) of a retention and drainage aid of 0.5g, adding 1g of cationic starch as an enhancer into the pulp suspension, stirring and mixing, and then performing die forming and hot press drying by using a rapid paper sheet forming technology to obtain the fiber suspension with a quantitative of 450g/m 2 Is a pulp molding material of (a).
From fig. 3, it can be observed that the pulp molding of the uncoated nano-chitin prepared in comparative example 1 is microscopically formed by interlacing fibers, and holes also occur in the interlacing fibers, and the holes contribute to the penetration of liquid.
From fig. 4, it can be observed that the pulp molding microscopic surface of the coated nano chitin obtained in example 4 is covered with a layer of nano chitin by the surface of the fiber, and the fiber interweaves to form pores, which are filled with the dried hydrophobic nano chitin, so as to achieve the purpose of tissue liquid infiltration.
From fig. 5, it can be seen that the pulp molding of the uncoated nano-chitin prepared in comparative example 1 is very water-absorbent, the surface water contact angle thereof is only 24.6 °, and finally water completely permeates into the pulp molding, which has a negative effect on the physical properties of the pulp molding.
As can be seen from fig. 6, the nano-chitin coated pulp molding obtained in example 4 has hydrophobicity, and its surface water contact angle reaches 108.3 °, which prevents penetration of water into the pulp molding, and can maintain physical properties of the pulp molding.
The antibacterial property of the pulp molding material was measured according to the method described by the national standard GBT 20944.1-2007-antibacterial property evaluation-agar plate method. FIG. 7 is divided into an upper half region and a lower half region, wherein the upper half region is the antibacterial effect of the 3 parallel samples of comparative example 1, and the lower half region is the antibacterial effect of the 3 parallel samples of example 4, and it can be found that the paper pulp molding material without nano-chitin coating can not influence the growth and propagation of bacterial colonies, while the paper pulp molding material sample coated with nano-chitin can form a distinct area for inhibiting the growth of bacterial colonies, i.e. bacterial colonies can not grow on or around the paper pulp molding material, which indicates that the nano-chitin coating has antibacterial effect.
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. A hydrophobic-antimicrobial pulp molding material characterized by: comprises a pulp molding material and a nano chitin coating coated on the pulp molding material.
2. A method for producing a pulp molding material as defined in claim 1, comprising the steps of:
firstly, adding filler into pulp fiber suspension, uniformly mixing, and carrying out mould forming and hot-press drying to obtain a pulp molding material; purifying and pre-treating chitin, deacetylating, homogenizing to obtain nanometer chitin dispersion; finally, spraying the obtained nano chitin dispersion liquid on the surface of the pulp molding material, and carrying out hot pressing and drying to obtain the hydrophobic-antibacterial pulp molding material.
3. The preparation method according to claim 2, characterized by comprising the following steps:
(1) Adding retention and drainage aids and reinforcing agents into pulp fiber suspension, and adopting a rapid paper sheet forming technology to obtain a pulp molding material through mold forming and hot press drying;
(2) Sequentially soaking, filtering and washing chitin in sodium hydroxide, hydrochloric acid and sodium hypochlorite solution, and finally drying to obtain bleached chitin;
(3) Adding the bleached chitin in the step (2) into a mixed solution of sodium borohydride and sodium hydroxide, heating, stirring, filtering and washing to obtain deacetylated chitin;
(4) Dispersing the deacetylated chitin prepared in the step (3) in water, adding acid to adjust pH, and homogenizing to obtain nano chitin dispersion;
(5) And (3) spraying the nano chitin dispersion liquid prepared in the step (4) to form a uniform coating on the surface of the pulp molding material, and performing hot pressing and drying to obtain the hydrophobic-antibacterial pulp molding material.
4. A method of preparation according to claim 3, characterized in that:
the source of pulp fibers in step (1) comprises at least one of bleached chemical pulp, unbleached chemical pulp, chemimechanical pulp, waste pulp; preferably at least one of waste pulp, bleached/unbleached kraft pulp, bleached/unbleached bagasse pulp, bleached/unbleached bamboo pulp, bleached/unbleached straw pulp, bleached/unbleached chemimechanical pulp.
5. A method of preparation according to claim 3, characterized in that:
the retention and drainage agent in the step (1) is at least one of polyacetylimide, polyamine, polyurethane and polyacrylamide;
the reinforcing agent in the step (1) is at least one of polyamide epichlorohydrin resin, melamine formaldehyde resin, urea formaldehyde resin, polyvinyl alcohol, carboxymethyl cellulose and cationic starch.
6. A method of preparation according to claim 3, characterized in that:
the mass of the retention and drainage aid in the step (1) is 0.01% -5% of the absolute dry mass of the pulp fibers; the mass of the reinforcing agent is 0.5-10% of the absolute dry mass of the pulp fiber;
the pulp fiber in the pulp molding material in the step (1) has the ration of 250-900 g/m 2 。
7. A method of preparation according to claim 3, characterized in that:
the mass concentration of sodium hydroxide in the mixed solution in the step (3) is 32% -38%; the mass ratio of the bleached chitin to the sodium borohydride is 1:0.02-0.06; the mass ratio of the bleached chitin to the sodium hydroxide is 1:10-50;
the heating temperature in the step (3) is 60-100 ℃, and the heating time is 1-5h.
8. A method of preparation according to claim 3, characterized in that:
the water dosage in the step (4) is as follows: so that the mass concentration of the nano chitin in the nano chitin dispersion liquid is 0.2-3%;
the acid in the step (4) is one of hydrochloric acid, formic acid and acetic acid; the pH value is adjusted to 3.5-4;
the conditions of the homogenization treatment in the step (4) are as follows: the homogenizing pressure is 500bar-1100bar, and the homogenizing times are 10 times-100 times.
9. A method of preparation according to claim 3, characterized in that:
the dosage of the nano chitin dispersion liquid in the step (5) is as follows: the mass of the nano chitin is 0.1-20% of the absolute dry mass of the pulp fiber; preferably 0.5% -10%.
10. Use of the pulp molding material of claim 1 in the field of packaging of food and daily chemicals.
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| CN202310431558.4A CN116590956A (en) | 2023-04-21 | 2023-04-21 | Hydrophobic-antibacterial pulp molding material, and preparation method and application thereof |
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