CN110983860B - Paper-based material surface coating agent, packaging paper and preparation method - Google Patents

Paper-based material surface coating agent, packaging paper and preparation method Download PDF

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CN110983860B
CN110983860B CN201911351132.8A CN201911351132A CN110983860B CN 110983860 B CN110983860 B CN 110983860B CN 201911351132 A CN201911351132 A CN 201911351132A CN 110983860 B CN110983860 B CN 110983860B
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paper
coating agent
surface coating
material surface
based material
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CN110983860A (en
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吴芹
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Qilu University of Technology
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Qilu University of Technology
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/42—Applications of coated or impregnated materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6492—Lignin containing materials; Wood resins; Wood tars; 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • 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
    • 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
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21H21/18—Reinforcing agents
    • 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

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Paper (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention provides a paper-based material surface coating agent, packaging paper and a preparation method thereof, wherein the paper-based material surface coating agent comprises the following preparation raw materials in parts by mass: 1-200 parts of lignin, 1-100 parts of isocyanate, 0.1-10 parts of dopamine or salt thereof, 0.1-10 parts of zinc salt and 0.1-10 parts of catalyst. The preparation method of the paper base material surface coating agent comprises the following steps: dissolving lignin, isocyanate, dopamine or salt thereof, zinc salt and a catalyst in a solvent, mixing, reacting, and evaporating the solvent to obtain the paper-based material surface coating agent. The paper-based material surface coating agent can obviously improve the strength, water resistance, oil resistance and antibacterial performance of the paper-based packaging material, and the used materials are all biodegradable materials, so the paper-based material surface coating agent is strong in environmental protection.

Description

Paper-based material surface coating agent, packaging paper and preparation method
Technical Field
The invention belongs to the technical field of papermaking chemicals, and particularly relates to a paper-based material surface coating agent, packaging paper and a preparation method.
Background
Under the double pressure of resources and environment, paper-based materials become an important development direction of green packaging materials due to the characteristics of recycling, cost saving, good processing and printing performances and the like. However, paper and paperboard are porous fiber materials, have low mechanical strength and have a certain degree of permeability to moisture, grease, and the like, and thus the range of use of a single paper packaging material is limited.
In order to meet the requirements of paper-based packaging materials on multifunction and high performance, a layer of functional material is usually coated on the surface of paper base, and the application and research of the functional coating material are focused on the following two materials: one is a synthetic polymer coating material, such as styrene-butadiene, acrylic acid, vinyl acetate and polyvinyl alcohol, and for styrene-butadiene and acrylic acid, although the styrene-butadiene and acrylic acid have better water resistance, oil resistance and mechanical properties, the degradation is slow in nature, so that the styrene-butadiene and acrylic acid are mainly incinerated at present, not only energy is wasted, but also the atmosphere is polluted; although vinyl acetate and polyvinyl alcohol are easy to degrade, but the water-resistant and moisture-proof performance is poor, Chinese patent document CN109667192A discloses a heat-insulating and heat-preserving packing paper and a preparation method thereof, wherein a coating layer of the packing paper comprises a PVA coating layer, the PVA coating layer comprises polyvinyl alcohol, aerogel, glycerol and sodium bicarbonate, and due to the poor waterproof performance of the polyvinyl alcohol, a PVB coating layer is also arranged on the PVA coating layer in the technology, the waterproof performance of the coating layer is improved through a PVB resin layer, but the composition of the coating layer is complex, and two layers of materials need to be coated; the other is natural high molecular coating material, such as starch, dextrin, chitin, cellulose, protein, etc. which has good hot processing performance and biodegradability but poor moisture-proof, waterproof and mechanical properties. In summary, the problems of the prior functional coating agent applied to paper-based packaging materials mainly include poor mechanical properties, single function, difficult degradation, poor environmental protection and the like.
Disclosure of Invention
The invention provides a paper-based material surface coating agent, a packaging paper and a preparation method thereof, and the coating agent can meet the requirements of paper-based packaging materials on strength, water resistance, oil resistance and antibacterial property, has a plurality of functions, and is easy to degrade.
In order to solve the problems, the invention provides a paper-based material surface coating agent, which comprises the following raw materials in parts by mass:
1-200 parts of lignin, 1-100 parts of isocyanate, 0.1-10 parts of dopamine or salt thereof, 0.1-10 parts of zinc salt and 0.1-10 parts of catalyst.
Preferably, the preparation raw materials of the paper base material surface coating agent comprise the following components in parts by mass:
30-80 parts of lignin, 20-50 parts of isocyanate, 1-5 parts of dopamine or salt thereof, 0.5-5 parts of zinc salt and 0.3-3 parts of catalyst.
Lignin is an amorphous aromatic high polymer widely existing in plants and containing structural units of oxyprophenyl alcohol or derivatives thereof in a molecular structure, belongs to a biodegradable material, contains functional groups such as phenolic hydroxyl, alcoholic hydroxyl and the like in a molecule and can provide active hydrogen atoms, and can be divided into guaiacyl type, syringyl type and p-hydroxyphenol type according to different monomers. Preferably, the lignin is one or more of guaiacol-based lignin, syringyl-based lignin and p-hydroxyphenol-based lignin.
The isocyanate refers to an ester compound which is formed by taking isocyanate as an acid radical and can react with active hydrogen in lignin molecules to generate a urethanization reaction to generate a lignin-based polyurethane prepolymer. Preferably, the isocyanate is one or a mixture of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate. The CAS number of hexamethylene diisocyanate is 822-06-0; the CAS number of isophorone diisocyanate is 4098-71-9; the CAS number of toluene diisocyanate is 584-84-9; diphenylmethane diisocyanate has a CAS number of 101-68-8.
Dopamine or its salt refers to dopamine or stable salt of dopamine, such as dopamine hydrochloride, dopamine is 4- (2-ethylamino) benzene-1, 2-diol, CAS number is 51-61-6, catechol and amino are contained in the molecule, active hydrogen is contained in both amino and phenolic hydroxyl, and the salt can react with-NCO in isocyanate molecule, and catechol structure in dopamine molecule has strong coordination effect on metal ions.
The zinc salt refers to inorganic salt or organic salt capable of ionizing zinc ions, and the zinc salt can be zinc chloride, zinc sulfate, zinc nitrate and the like, preferably, the zinc salt is zinc chloride.
Preferably, the catalyst is an organic tin catalyst, and the organic tin catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfur) and dibutyltin diacetate. The CAS number of dibutyltin dilaurate is 77-58-7; stannous octoate is also known as 2-ethyl stannous hexanoate, and the CAS number is 301-10-0; the CAS number of dibutyltin bis (dodecyl sulfur) is 1185-81-5; no. 1067-33-0 of dibutyltin diacetate CAS.
According to the paper-based material surface coating agent, in reaction raw materials, lignin molecules contain a large amount of active hydrogen, and can perform a urethanization reaction with partial-NCO in isocyanate in the presence of a catalyst to generate a lignin-based polyurethane prepolymer containing carbamate (-NH-COO-), dopamine molecules contain catechol and amino with active hydrogen and can react with the-NCO in the rest part of isocyanate in the lignin-based polyurethane prepolymer, dopamine is grafted on the lignin-based polyurethane prepolymer, and zinc ions ionized by zinc salts can structurally form coordinate bonds with the catechol in the dopamine molecules, so that the zinc ions are grafted on the lignin-based polyurethane prepolymer to obtain the paper-based material surface coating agent. The structure of the coating agent on the surface of the paper base material contains carbamate formed by reaction of lignin and isocyanate, the formed coating has good strength, water resistance and oil resistance, the lignin has a three-dimensional structure, the crosslinking density and strength of the coating agent can be further increased, the water resistance of the coating agent can be further improved, the catechol structure in the lignin and dopamine can stop free radicals generated by the coating agent under the influence of the external environment, the ageing resistance of the coating agent is improved, the zinc forming a coordinate bond with the catechol structure of dopamine can enable the coating agent to have certain antibacterial performance, the dopamine also has good adhesiveness, a cementing material does not need to be added into the coating agent, the coating process is simpler, in addition, the raw materials in the coating agent are degradable materials, and the environment-friendly performance is high.
Another object of the present invention is to provide a method for preparing the above paper-based material surface coating agent, comprising the steps of:
dissolving lignin, isocyanate, dopamine or salt thereof, zinc salt and a catalyst in a solvent, mixing, reacting, and evaporating the solvent to obtain the paper-based material surface coating agent.
Preferably, the method comprises the following steps:
s1, dissolving lignin, isocyanate and a catalyst in a solvent, and mixing to perform a urethanization reaction;
s2, adding dopamine or dopamine salt into the product obtained in the step S1, and mixing to react;
s3, adding zinc salt into the product obtained in the step S2, mixing, and carrying out coordination reaction;
and S4, evaporating the product obtained in the step S3 to dryness to obtain the paper-based material surface coating agent.
Preferably, the reaction temperature of the urethanization reaction of the step S1 is 60-85 ℃, and the reaction time is 4-24 h.
Further preferably, the stirring rate in the urethanization reaction of step S1 is 200-400 r/min.
Preferably, the reaction temperature of step S2 is 50-60 ℃, and the reaction time is 2-4 h.
Further preferably, the stirring rate during the reaction of step S2 is 200-400 r/min.
Preferably, the reaction temperature of step S3 is 50-60 ℃ and the reaction time is 0.5-2 h.
Further preferably, the stirring rate in the coordination reaction of step S3 is 200-400 r/min.
Preferably, the solvent is N, N-dimethylformamide.
Dissolving lignin and isocyanate in a solvent, adding a catalyst, reacting active hydrogen in lignin molecules with partial-NCO in the isocyanate under the action of the catalyst to generate a lignin-based polyurethane prepolymer containing carbamate, adding dopamine, reacting amino in the dopamine and active hydrogen in catechol with-NCO in the rest part of the isocyanate, embedding a dopamine functional group in the lignin-based polyurethane prepolymer, adding a zinc salt, grafting Zn on the lignin-based prepolymer by utilizing the coordination bond action of the catechol in the dopamine2+To obtain lignin-based polyurethane-dopamine-Zn2+The copolymer is dried by distillation to obtain the coating agent.
Still another object of the present invention is to provide a wrapping paper comprising a paper-based material, the surface of which is coated with the above-mentioned paper-based material surface coating agent.
Compared with the prior art, the invention has the following beneficial effects:
1. the structure of the paper-based material surface coating agent contains carbamate formed by reaction of lignin and isocyanate, the formed coating has good strength, water resistance and oil resistance, and the lignin has a three-dimensional structure, so that the crosslinking density and strength of the coating agent can be further increased, and the water resistance of the coating agent is further improved; dopamine is grafted on the lignin-based polyurethane prepolymer through the reaction of active hydrogen and isocyanate, the catechol structure in lignin and dopamine can stop free radicals generated by a coating agent under the influence of an external environment, the ageing resistance of the coating agent is improved, the dopamine also has good adhesiveness, and a cementing material is not required to be added into the coating agent, so that the coating process is simpler, the operation is easy, the pollution is less, the efficiency is high, and the safety is high; the catechol structure in dopamine molecules can form a coordinate bond with zinc ions, and the zinc ions are grafted on the lignin-based polyurethane prepolymer, so that the coating agent has certain antibacterial performance; in addition, the raw materials in the coating agent are all biodegradable materials, so that the coating agent is high in environmental protection;
2. the method for preparing the paper-based material surface coating agent has simple preparation process, and ensures that the reaction conversion rate of lignin and isocyanate in the obtained product is higher and dopamine and Zn are contained by controlling the reaction temperature, time and stirring rate of three reactions in the preparation process2+The grafting rate is higher, so that the mechanical strength is higher, the water resistance and the oil resistance are better, and the antibacterial effect is better after the coating agent is coated on a paper base material.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate were obtained from sigma-aldrich; dopamine hydrochloride was purchased from alatin reagent; dibutyl tin dilaurate, stannous octoate, dibutyl tin diacetate, and dibutyl tin bis (dodecyl sulfur) were purchased from Woodward chemical Co., Ltd, and the remaining raw materials were purchased from the market.
It should be noted that the above-mentioned raw material sources are only examples, and the actual selection is not unique, and those skilled in the art can also purchase products of other manufacturers and specifications according to the actual situation, and the implementation of the technical effects of the present invention is not affected by the products of different manufacturers and specifications.
Example one
The paper base material surface coating agent described in this example was prepared from the following ingredients: 5g of guaiacol-based lignin, 2g of hexamethylene diisocyanate, 0.1g of dopamine hydrochloride, 0.15g of zinc chloride and 0.1g of dibutyltin dilaurate.
The preparation method of the paper-based material surface coating agent of the embodiment is specifically as follows:
s1, mixing guaiacol-based lignin and hexamethylene diisocyanate, dissolving the mixture in 100ml of N, N-dimethylformamide, adding dibutyltin dilaurate into the mixed solution, controlling the reaction temperature to be 65 ℃, stirring at the speed of 250r/min, and stopping the reaction after reacting for 16 hours to obtain a lignin-based polyurethane prepolymer;
s2, adding dopamine hydrochloride into the product obtained in the step S1, mixing, controlling the reaction temperature to be 55 ℃, controlling the stirring speed to be 200r/min, and stopping the reaction after reacting for 4 hours to enable dopamine to be embedded into the lignin-based polyurethane prepolymer;
s3, adding zinc chloride into the product obtained in the step S2, mixing, controlling the reaction temperature at 50 ℃, stirring at a speed of 300r/min, stopping the reaction after 1h, and grafting Zn onto the lignin-based polyurethane prepolymer2+；
S4, evaporating the solvent of the product obtained in the step S3 to obtain the paper-based material surface coating agent.
Example two
The paper base material surface coating agent described in this example was prepared from the following ingredients: 4g of syringyl lignin, 2.5g of isophorone diisocyanate, 0.2g of dopamine hydrochloride, 0.25g of zinc chloride and 0.15g of stannous octoate.
The preparation method of the paper base material surface coating agent of the embodiment is specifically as follows:
s1, mixing syringyl lignin and isophorone diisocyanate, dissolving the mixture in 100ml of N, N-dimethylformamide, adding stannous octoate into the mixed solution, controlling the reaction temperature to be 70 ℃, stirring at the speed of 300r/min, and stopping the reaction after the reaction is carried out for 14 hours to obtain a lignin-based polyurethane prepolymer;
s2, adding dopamine hydrochloride into the product obtained in the step S1, mixing, controlling the reaction temperature to be 50 ℃, controlling the stirring speed to be 300r/min, and stopping the reaction after reacting for 3 hours to enable the dopamine to be embedded into the lignin-based polyurethane prepolymer;
s3, adding zinc chloride into the product obtained in the step S2, mixing, controlling the reaction temperature to be 55 ℃, controlling the stirring speed to be 250r/min, stopping the reaction after 0.5h, and grafting Zn on the lignin-based polyurethane prepolymer2+；
And S4, evaporating the product obtained in the step S3 to dryness to obtain the paper-based material surface coating agent.
EXAMPLE III
The paper base material surface coating agent described in this example was prepared from the following ingredients: 6g of p-hydroxyphenol-type lignin, 3g of toluene diisocyanate, 0.3g of dopamine hydrochloride, 0.3g of zinc chloride and 0.2g of dibutyltin diacetate.
The preparation method of the paper base material surface coating agent of the embodiment is specifically as follows:
s1, mixing p-hydroxyphenol-type lignin and toluene diisocyanate, dissolving the mixture in 100ml of N, N-dimethylformamide, adding dibutyltin diacetate into the mixed solution, controlling the reaction temperature to be 75 ℃, stirring at the speed of 200r/min, and stopping the reaction after reacting for 10 hours to obtain a lignin-based polyurethane prepolymer;
s2, adding dopamine hydrochloride into the product obtained in the step S1, mixing, controlling the reaction temperature to be 60 ℃, controlling the stirring speed to be 250r/min, and stopping the reaction after reacting for 2.5 hours to enable dopamine to be embedded into the lignin-based polyurethane prepolymer;
s3, adding zinc chloride into the product obtained in the step S2, mixing, controlling the reaction temperature at 60 ℃, stirring at the speed of 250r/min, and stopping reaction after 1.5 hours of reactionGrafting Zn onto lignin-base polyurethane prepolymer2+；
And S4, evaporating the product obtained in the step S3 to dryness to obtain the paper-based material surface coating agent.
Example four
The paper base material surface coating agent described in this example was prepared from the following ingredients: 7.5g of p-hydroxyphenol-type lignin, 3.2g of diphenylmethane diisocyanate, 0.25g of dopamine hydrochloride, 0.2g of zinc chloride and 0.22g of dibutyltin dilauryl sulfide.
The preparation method of the paper base material surface coating agent of the embodiment is specifically as follows:
s1, mixing p-hydroxyphenol-type lignin and diphenylmethane diisocyanate, dissolving the mixture in 100ml of N, N-dimethylformamide, adding dibutyltin dilauryl sulfide into the mixed solution, controlling the reaction temperature to be 80 ℃, stirring at the speed of 350r/min, and stopping the reaction after reacting for 8 hours to obtain a lignin-based polyurethane prepolymer;
s2, adding dopamine hydrochloride into the product obtained in the step S1, mixing, controlling the reaction temperature to be 55 ℃, controlling the stirring speed to be 350r/min, and stopping the reaction after reacting for 2 hours to enable the dopamine to be embedded into the lignin-based polyurethane prepolymer;
s3, adding zinc chloride into the product obtained in the step S2, mixing, controlling the reaction temperature to be 55 ℃, stirring at the speed of 200r/min, stopping the reaction after 2 hours of reaction, and grafting Zn on the lignin-based polyurethane prepolymer2+；
And S4, evaporating the product obtained in the step S3 to dryness to obtain the paper-based material surface coating agent.
EXAMPLE five
The paper base material surface coating agent described in this example was prepared from the following ingredients: 3g of guaiacol-based lignin, 4g of hexamethylene diisocyanate, 0.5g of dopamine hydrochloride, 0.05g of zinc chloride and 0.03g of dibutyltin dilaurate. The preparation method of the paper base material surface coating agent of the embodiment is the same as that of the embodiment one.
EXAMPLE six
The paper base material surface coating agent described in this example was prepared from the following ingredients: 8g of guaiacol-based lignin, 5g of hexamethylene diisocyanate, 0.4g of dopamine hydrochloride, 0.5g of zinc chloride and 0.3g of dibutyltin dilaurate. The preparation method of the paper base material surface coating agent of the embodiment is the same as that of the embodiment one.
EXAMPLE seven
The paper base material surface coating agent described in this example was prepared from the following ingredients: 1g of guaiacol-based lignin, 1g of hexamethylene diisocyanate, 1g of dopamine hydrochloride, 0.01g of zinc chloride and 0.01g of dibutyltin dilaurate. The preparation method of the paper base material surface coating agent of the embodiment is the same as that of the embodiment one.
Example eight
The paper base material surface coating agent described in this example was prepared from the following ingredients: 15g of guaiacol-based lignin, 8g of hexamethylene diisocyanate, 0.01g of dopamine hydrochloride, 1g of zinc chloride and 1g of dibutyltin dilaurate. The preparation method of the paper base material surface coating agent of the embodiment is the same as that of the embodiment one.
Example nine
The paper base material surface coating agent described in this example was prepared from the following ingredients: 20g of guaiacol-based lignin, 10g of hexamethylene diisocyanate, 0.04g of dopamine hydrochloride, 0.03g of zinc chloride and 0.02g of dibutyltin dilaurate. The preparation method of the paper base material surface coating agent of the embodiment is the same as that of the embodiment one.
Example ten
The composition of the raw materials for preparing the paper-based material surface coating agent described in this example is the same as that in example one.
The preparation method of the surface coating agent of a paper-based material of this example was the same as in example one except that the reaction temperature was 60 c and the reaction time was 24h in step S1.
EXAMPLE eleven
The composition of the raw materials for preparing the paper-based material surface coating agent described in this example is the same as that in example one.
The preparation method of the surface coating agent of a paper-based material of this example was the same as in example one except that the reaction temperature in step S1 was 85 deg.c and the reaction time was 4 hours.
Example twelve
The paper base material surface coating agent of the embodiment has the same preparation raw material composition as that of the embodiment one.
The preparation method of the surface coating agent of the paper base material of the present example is the same as that of the first example, except that the reaction temperature in the step S1 is 40 ℃, and the reaction time is 28 hours; the reaction temperature of the step S2 is 40 ℃, and the reaction time is 5 h; the reaction temperature of step S3 was 40 ℃ and the reaction time was 3 h.
EXAMPLE thirteen
The composition of the raw materials for preparing the paper-based material surface coating agent described in this example is the same as that in example one.
The preparation method of the paper-based material surface coating agent of this example is the same as that of example one, except that the reaction temperature in step S1 is 90 ℃, and the reaction time is 4 hours; the reaction temperature of the step S2 is 70 ℃, and the reaction time is 1 h; the reaction temperature of step S3 was 70 ℃ and the reaction time was 0.5 h.
Paper base material surface coating agent performance test
The performance of the paper-based material surface coating agent obtained in each of the above examples was tested by the following method: by manual coating method, each coating agent is coated by 10g/m with a brush2The coating weight of (A) was 70g/m2The surface of the paper is coated along one direction, after leveling, the paper is dried for 3min by infrared at 150 ℃ to obtain a coated paper sheet, the performance of the paper sheet is tested to obtain the performance of the coating agent on the surface of the paper base material, and the comparative example is the paper which is not coated with the coating agent.
And (3) testing the strength of the paper: the strength performance of the paper is measured by the national standard GB/T12914 + 2008 'determination of tensile strength of paper and paperboard', and the breaking length of the paper is measured.
Testing the water absorption performance of the paper surface: the surface water absorption property of the paper is measured by the national standard method GB/T1540-2002 'determination of paper and paperboard water absorption' and the Cobb value (surface water absorption value) of the paper is measured.
Testing the bacteriostatic performance of the paper: the antibacterial performance of the coating agent is determined by adopting an antibacterial ring method, a certain amount of bacterial suspension with proper concentration is taken and evenly coated on a sterilized nutrient agar plate by a coating method, an uncoated paper sample with the diameter of 16mm and a coated paper sample are respectively placed on the plate of a nutrient agar solid culture medium with the surface coated with bacteria, then a culture dish is placed in a constant-temperature incubator at 37 ℃ for culture for 24 hours, and the antibacterial performance of the coating agent is evaluated by the diameter of an antibacterial ring.
The results of the paper property test after coating with the coating agent of each example are shown in table 1, and the results in table 1 show that the paper base material coated with the surface coating agent of the paper base material of the invention has significantly improved mechanical properties, surface water resistance and antibacterial properties compared with the uncoated paper base material, the breaking length of the paper is improved from uncoated 1.654km to 2.221-3.264km, and the surface water absorption value is improved from uncoated 22.4g/m2Reduced to 47-13.1g/m2The diameter of the inhibition zone for gram-positive bacteria is increased from 0 to 32-13.2mm, and the diameter of the inhibition zone for gram-negative bacteria is increased from 0 to 3.1-12.6 mm; furthermore, the first, second, third, fourth, fifth, sixth, tenth and eleventh embodiments are the preferred embodiments of the present invention, and within the preferred range of raw material composition and preparation process parameters, the paper base material coated with the surface coating agent has a breaking length of 3.047-3.264km and a surface water absorption value of 4.7-6.8g/m2The diameter of the inhibition zone for gram-positive bacteria can reach 12.5-13.2mm, and the diameter of the inhibition zone for gram-negative bacteria can reach 11.3-12.6 mm.
TABLE 1
Figure BDA0002334688270000101
Figure BDA0002334688270000111
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (5)

1. The paper base material surface coating agent is characterized in that the preparation raw materials of the paper base material surface coating agent comprise the following components in parts by mass:
30-80 parts of lignin, 20-50 parts of isocyanate, 1-5 parts of dopamine or salt thereof, 0.5-5 parts of zinc salt and 0.3-3 parts of catalyst; the catalyst is an organic tin catalyst; the zinc salt is one or a mixture of zinc chloride, zinc sulfate and zinc nitrate;
the preparation method of the paper base material surface coating agent comprises the following steps:
s1, dissolving lignin, isocyanate and a catalyst in a solvent, and mixing to perform a urethanization reaction;
s2, adding dopamine or dopamine salt into the product obtained in the step S1, mixing, and reacting at 50-60 ℃ for 2-4 h;
s3, adding zinc salt into the product obtained in the step S2, mixing, and carrying out coordination reaction at the temperature of 50-60 ℃ for 0.5-2 h;
and S4, evaporating the product obtained in the step S3 to dryness to obtain the paper-based material surface coating agent.
2. A surface coating agent of a paper based material as claimed in claim 1, characterized in that:
the isocyanate is one or a mixture of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate.
3. A surface coating agent of a paper based material as claimed in claim 1, characterized in that:
the organic tin catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, dibutyltin didodecyl sulfide and dibutyltin diacetate.
4. A surface coating agent of a paper based material according to any one of claims 1 to 3, characterized in that:
the reaction temperature of the urethane reaction of the step S1 is 60-85 ℃, and the reaction time is 4-24 h.
5. A wrapping paper comprising a paper-based material having a surface coated with the paper-based material surface coating agent as claimed in any one of claims 1 to 3.
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