CN113774716A - Multifunctional auxiliary agent for improving paper strength and preparation method thereof - Google Patents

Multifunctional auxiliary agent for improving paper strength and preparation method thereof Download PDF

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Publication number
CN113774716A
CN113774716A CN202111048574.2A CN202111048574A CN113774716A CN 113774716 A CN113774716 A CN 113774716A CN 202111048574 A CN202111048574 A CN 202111048574A CN 113774716 A CN113774716 A CN 113774716A
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lignin
stirring
improving
dispersion liquid
phosphogypsum
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Chinese (zh)
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周春松
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Fuquan Environmental Protection Co ltd
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Fuquan Environmental Protection Co ltd
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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
    • 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
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
    • 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
    • D21H17/23—Lignins
    • 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
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • 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
    • D21H17/67—Water-insoluble compounds, e.g. fillers, 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material

Abstract

The invention discloses a multifunctional auxiliary agent for improving paper strength, which is prepared by pre-polymerizing tannic acid, lignin and hexamethylene diisocyanate, adding polyethylene glycol for cross-linking reaction, and finally mixing with modified phosphogypsum whiskers; the modified phosphogypsum whisker is prepared by sequentially treating the pretreated phosphogypsum whisker by phosphoric acid and ammonia water. The invention also discloses a preparation method of the multifunctional auxiliary agent, and the prepared multifunctional auxiliary agent has good binding performance with a paper substrate and can effectively improve the strength of paper.

Description

Multifunctional auxiliary agent for improving paper strength and preparation method thereof
Technical Field
The invention relates to the technical field of papermaking, in particular to a multifunctional auxiliary agent for improving paper strength and a preparation method thereof
Background
Food products are extremely susceptible to contamination by oxygen, moisture, light, dust, and chemicals and microorganisms during storage, transportation, and sale, resulting in inedible food and thus huge food waste. Food packaging is commonly used in the food industry to protect food from unnecessary environmental interference, petroleum-based disposable packaging is mostly occupied in the food packaging industry at home and abroad, and used materials are not easy to biodegrade and are easy to accumulate in the environment, so that serious environmental pollution and food safety problems are caused. Paper, as a biodegradable material, has been widely used in the field of food packaging due to its low cost, convenient use and ability to better protect the packaged product. But the lack of functionality of conventional paper-based materials has greatly limited their use. In order to expand the application range of paper base materials, methods such as coating, dipping, adding in pulp, fiber grafting modification and the like are generally adopted to improve the paper performance. Among them, the coating method is the most economical and effective method, and is receiving increasing attention.
The phosphogypsum is CaSO discharged by phosphorus chemical enterprises in the process of producing ammonium phosphate fertilizer or producing phosphoric acid by a wet method4·2H2O is an industrial byproduct with a main component. The application of the phosphogypsum whisker prepared from the phosphogypsum in the papermaking industry mainly considers two main attack directions, namely, the phosphogypsum whisker is used as a paper filler or a coating pigment, and the phosphogypsum whisker is used for the paper filler, so that the bulk of paper can be improved, the production cost is reduced, but the solubility of the phosphogypsum whisker is higher, the retention rate of the filler is lower, and the white water load is increased in the white water circulation process; the phosphogypsum whisker is used for the paper-making coating pigment, so that the comprehensive utilization rate of phosphorite waste can be improved, natural mineral resources are protected, the problem of the solubility of the whisker is basically not considered in the use process, the development of a novel coating pigment in the paper-making industry is facilitated, and the development of a paper-making coating technology is promoted. However, how to improve the binding performance of the coating material and the paper and the coating materialThe interface performance of each component in the material becomes the key for the research of coating technology.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the invention provides a multifunctional auxiliary agent for improving the paper strength and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a multifunctional assistant for improving the strength of paper is prepared by pre-polymerizing tannic acid, lignin and hexamethylene diisocyanate, adding polyethylene glycol for cross-linking reaction, and mixing with modified phosphogypsum whiskers; the modified phosphogypsum whisker is prepared by sequentially treating the pretreated phosphogypsum whisker by phosphoric acid and ammonia water.
Preferably, the preparation method of the modified phosphogypsum whisker comprises the following steps: cleaning phosphogypsum with clear water, dispersing in water again, adding quicklime, stirring, and filtering; dispersing the pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.15-0.25g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 9-10, stirring and reacting for 1-3h after dripping is finished, then filtering, and washing the obtained precipitate to prepare the modified phosphogypsum whisker.
Preferably, in the technical scheme, the mass ratio of the phosphogypsum to the quick lime is 50: (1-2); the stirring treatment time is 30-60 min.
In order to better solve the technical problems, the invention also provides the following technical scheme:
a preparation method of a multifunctional auxiliary agent for improving the strength of paper comprises the following steps:
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution and a tannic acid solution, respectively adding hexamethylene diisocyanate into the lignin solution and the tannic acid solution to perform prepolymerization to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding polyethylene glycol, stirring and crosslinking at room temperature, adding the dimethyl sulfoxide dispersion liquid of the modified phosphogypsum whisker, and stirring and mixing to prepare the multifunctional additive.
Preferably, the lignin has an average molecular weight of 5170 and a polydispersity of 2.16; the polyethylene glycol is polyethylene glycol 400.
Preferably, the concentrations of the lignin solution and the tannic acid solution are 15-20 wt% and 3-5 wt%, respectively.
Preferably, the temperature of the prepolymerization is 50-60 ℃, and the time of the prepolymerization is 30-40 min.
Preferably, in the above technical solution, the mass ratio of the hexamethylene diisocyanate, the polyethylene glycol, the lignin and the tannic acid is 3.5: 3: (1-2): (0.2-0.4).
Preferably, the rotation speed of the stirring crosslinking reaction is 1500-.
Preferably, in the technical scheme, the concentration of the dimethyl sulfoxide dispersion liquid of the modified phosphogypsum whisker is 5-10 wt%, and the mass ratio of the modified phosphogypsum whisker to the lignin is (0.25-0.45): 1, the stirring and mixing time is 30-60 min.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, lignin and hexamethylene diisocyanate are mixed for a prepolymerization reaction, and hydroxyl in the lignin can be subjected to a crosslinking reaction with isocyanate groups in the hexamethylene diisocyanate; the tannin and the hexamethylene diisocyanate are mixed for prepolymerization reaction, hydroxyl at the tail end of a tannin molecule can also be subjected to crosslinking reaction with an isocyanate group in the hexamethylene diisocyanate, and finally polyethylene glycol is added for crosslinking at room temperature to prepare a tannin and a lignin modified polyurethane matrix, wherein the tannin and the lignin are introduced into the modified polyurethane in the form of an active chain segment, so that the performance of the polyurethane is improved. The modified phosphogypsum crystal whisker is added, and can realize good dispersion in a polyurethane matrix under the action of tannic acid.
When the multifunctional auxiliary agent prepared by the invention is used for paper coating, the multifunctional auxiliary agent can effectively permeate into paper fibers, and the bonding force between the fibers is improved, so that the strength of the paper is improved. And the modification of the lignin and the tannic acid also improves the ultraviolet resistance of the paper.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
Cleaning 50g of phosphogypsum with 500ml of clear water, dispersing the phosphogypsum in 500ml of water again, adding 1g of quicklime, stirring for 30min, and filtering; dispersing pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.15g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 9, stirring for reacting for 1h after the dropwise adding is finished, then filtering, and washing the obtained precipitate to prepare the modified phosphogypsum whisker with the diameter of 1 mu m and the length of 13 mu m;
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution with the concentration of 20 wt% and a tannic acid solution with the concentration of 5 wt%, respectively adding 3.5g of hexamethylene diisocyanate into 10g of the lignin solution and 8g of the tannic acid solution, and performing prepolymerization at 50 ℃ for 30min to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding 3g of polyethylene glycol, stirring at room temperature and at the rotating speed of 1500 rpm, carrying out crosslinking reaction for 1h, adding 7g of dimethyl sulfoxide dispersion liquid of modified phosphogypsum whiskers with the concentration of 10 wt%, and stirring and mixing for 30min to obtain the multifunctional additive.
Example 2
Cleaning 50g of phosphogypsum with 500ml of clear water, dispersing in 500ml of water again, adding 1.5g of quicklime, stirring for 60min, and filtering; dispersing the pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.2g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 9, stirring and reacting for 1.5h after the dropwise adding is finished, filtering, and washing the obtained precipitate to prepare the modified phosphogypsum whisker with the diameter of 1.5 mu m and the length of 13.5 mu m;
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution with the concentration of 20 wt% and a tannic acid solution with the concentration of 5 wt%, respectively adding 3.5g of hexamethylene diisocyanate into 10g of the lignin solution and 8g of the tannic acid solution, and performing prepolymerization at 50 ℃ for 30min to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding 3g of polyethylene glycol, stirring at room temperature and 2000 rpm for crosslinking reaction for 2h, adding 7g of 10 wt% modified phosphogypsum whisker dimethyl sulfoxide dispersion liquid, and stirring and mixing for 40min to obtain the multifunctional additive.
Example 3
Cleaning 50g of phosphogypsum with 500ml of clear water, dispersing the phosphogypsum in 500ml of water again, adding 1g of quicklime, stirring for 40min, and filtering; dispersing pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.2g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 10, stirring and reacting for 3 hours after the dropwise adding is finished, then filtering, and washing the obtained precipitate to prepare modified phosphogypsum whiskers with the diameter of 1 mu m and the length of 13.5 mu m;
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution with the concentration of 20 wt% and a tannic acid solution with the concentration of 5 wt%, respectively adding 3.5g of hexamethylene diisocyanate into 10g of the lignin solution and 8g of the tannic acid solution, and carrying out prepolymerization at 55 ℃ for 30min to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding 3g of polyethylene glycol, stirring and crosslinking for 1h at room temperature and at the rotating speed of 2500 rpm, then adding 7g of dimethyl sulfoxide dispersion liquid of modified phosphogypsum whiskers with the concentration of 10 wt%, and stirring and mixing for 30min to obtain the multifunctional additive.
Example 4
Cleaning 50g of phosphogypsum with 500ml of clear water, dispersing in 500ml of water again, adding 2g of quicklime, stirring for 50min, and filtering; dispersing pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.15g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 10, stirring for reacting for 2 hours after the dropwise adding is finished, then filtering, and washing the obtained precipitate to prepare modified phosphogypsum whiskers with the diameter of 2 microns and the length of 13 microns;
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution with the concentration of 20 wt% and a tannic acid solution with the concentration of 5 wt%, respectively adding 3.5g of hexamethylene diisocyanate into 10g of the lignin solution and 8g of the tannic acid solution, and carrying out prepolymerization at 55 ℃ for 30min to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding 3g of polyethylene glycol, stirring and crosslinking for 2 hours at room temperature and at the rotating speed of 3500 rpm, then adding 7g of dimethyl sulfoxide dispersion liquid of modified phosphogypsum whiskers with the concentration of 10 wt%, and stirring and mixing for 30 minutes to obtain the multifunctional additive.
Example 5
Cleaning 50g of phosphogypsum with 500ml of clear water, dispersing the phosphogypsum in 500ml of water again, adding 2g of quicklime, stirring for 60min, and filtering; dispersing pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.25g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 10, stirring and reacting for 3 hours after the dropwise adding is finished, then filtering, and washing the obtained precipitate to prepare modified phosphogypsum whiskers with the diameter of 1.5 microns and the length of 13.2 microns;
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution with the concentration of 20 wt% and a tannic acid solution with the concentration of 5 wt%, respectively adding 3.5g of hexamethylene diisocyanate into 10g of the lignin solution and 8g of the tannic acid solution, and performing prepolymerization at 50 ℃ for 30min to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding 3g of polyethylene glycol, stirring and carrying out crosslinking reaction for 3 hours at room temperature and at the rotating speed of 3500 rpm, then adding 7g of dimethyl sulfoxide dispersion liquid of modified phosphogypsum whiskers with the concentration of 10 wt%, and stirring and mixing for 60 minutes to obtain the multifunctional additive.
Comparative example
Cleaning 50g of phosphogypsum with 500ml of clear water, dispersing the phosphogypsum in 500ml of water again, adding 2g of quicklime, stirring for 60min, and filtering; dispersing pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.25g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 10, stirring and reacting for 3 hours after the dropwise adding is finished, then filtering, and washing the obtained precipitate to prepare modified phosphogypsum whiskers with the diameter of 1.5 microns and the length of 13.2 microns;
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to prepare a lignin solution with the concentration of 20 wt% and a tannic acid solution with the concentration of 5 wt%, mixing 10g of the lignin solution, 8g of the tannic acid solution, 3.5g of hexamethylene diisocyanate and 3g of polyethylene glycol, then adding 0.07g of dibutyltin dilaurate to react for 210min at the temperature of 50 ℃, then cooling to room temperature, adding 7g of dimethyl sulfoxide dispersion liquid of modified phosphogypsum whiskers with the concentration of 10 wt%, and stirring and mixing for 60min to prepare the multifunctional assistant.
The multifunctional auxiliary agent prepared in the above examples and comparative examples is coated on the surface of the fiber paper by adopting a ZY-YB-B4 coating machine, and the coating weight is 10g/m3And curing, and testing the performance of the prepared coated paper. The results are shown in Table 1.
TABLE 1
Figure BDA0003251963170000061
Figure BDA0003251963170000071
From the above test results, it can be seen that the multifunctional assistant prepared by pre-polymerizing lignin, tannic acid and hexamethylene diisocyanate of the present invention can effectively improve the strength of paper.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Claims (10)

1. The multifunctional assistant for improving the strength of paper is characterized in that: the multifunctional auxiliary agent is prepared by pre-polymerizing tannic acid, lignin and hexamethylene diisocyanate, adding polyethylene glycol for cross-linking reaction, and mixing with modified phosphogypsum whisker; the modified phosphogypsum whisker is prepared by sequentially treating the pretreated phosphogypsum whisker by phosphoric acid and ammonia water.
2. The multifunctional assistant for improving paper strength according to claim 1, wherein: the preparation method of the modified phosphogypsum whisker comprises the following steps: cleaning phosphogypsum with clear water, dispersing in water again, adding quicklime, stirring, and filtering; dispersing the pretreated phosphogypsum in water to prepare a dispersion liquid with the concentration of 0.15-0.25g/ml, adding phosphoric acid into the dispersion liquid to adjust the pH value of the dispersion liquid to be 1, then adding ammonia water under the stirring condition to adjust the pH value of the dispersion liquid to be 9-10, stirring and reacting for 1-3h after dripping is finished, then filtering, and washing the obtained precipitate to prepare the modified phosphogypsum whisker.
3. The multifunctional assistant for improving paper strength according to claim 2, wherein: the mass ratio of the phosphogypsum to the quick lime is 50: (1-2); the stirring treatment time is 30-60 min.
4. The method for preparing the multifunctional assistant for improving the paper strength according to any one of claims 1 to 3, characterized by comprising the following steps:
respectively dissolving lignin and tannic acid in dimethyl sulfoxide to obtain a lignin solution and a tannic acid solution, respectively adding hexamethylene diisocyanate into the lignin solution and the tannic acid solution to perform prepolymerization to obtain a prepolymer A and a prepolymer B; and mixing the prepolymer A and the prepolymer B, adding polyethylene glycol, stirring and crosslinking at room temperature, adding the dimethyl sulfoxide dispersion liquid of the modified phosphogypsum whisker, and stirring and mixing to prepare the multifunctional additive.
5. The method for preparing the multifunctional assistant for improving the paper strength according to claim 4, wherein the method comprises the following steps: the average molecular weight of the lignin is 5170, and the polydispersity index of the lignin is 2.16; the polyethylene glycol is polyethylene glycol 400.
6. The method for preparing the multifunctional assistant for improving the paper strength according to claim 4, wherein the method comprises the following steps: the concentrations of the lignin solution and the tannic acid solution are respectively 15-20 wt% and 3-5 wt%.
7. The method for preparing the multifunctional assistant for improving the paper strength according to claim 4, wherein the method comprises the following steps: the temperature of the prepolymerization is 50-60 ℃, and the time of the prepolymerization is 30-40 min.
8. The method for preparing the multifunctional assistant for improving the paper strength according to claim 4, wherein the method comprises the following steps: the mass ratio of the hexamethylene diisocyanate to the polyethylene glycol to the lignin to the tannic acid is 3.5: 3: (1-2): (0.2-0.4).
9. The method for preparing the multifunctional assistant for improving the paper strength according to claim 4, wherein the method comprises the following steps: the rotation speed of the stirring crosslinking reaction is 1500-.
10. The method for preparing the multifunctional assistant for improving the paper strength according to claim 4, wherein the method comprises the following steps: the concentration of the dimethyl sulfoxide dispersion liquid of the modified phosphogypsum whisker is 5-10 wt%, and the mass ratio of the modified phosphogypsum whisker to lignin is (0.25-0.45): 1, the stirring and mixing time is 30-60 min.
CN202111048574.2A 2021-09-08 2021-09-08 Multifunctional auxiliary agent for improving paper strength and preparation method thereof Pending CN113774716A (en)

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