CN110685185A - Preparation method of environment-friendly paper oil-proof agent - Google Patents

Preparation method of environment-friendly paper oil-proof agent Download PDF

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CN110685185A
CN110685185A CN201911063209.1A CN201911063209A CN110685185A CN 110685185 A CN110685185 A CN 110685185A CN 201911063209 A CN201911063209 A CN 201911063209A CN 110685185 A CN110685185 A CN 110685185A
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mixing
mass
mass ratio
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黄淑芬
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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/50—Proteins
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)

Abstract

The invention discloses a preparation method of an environment-friendly paper oil-proofing agent, belonging to the technical field of papermaking additives. Mixing the concentrate with toluene according to a mass ratio of 1: 2-1: 3, mixing, standing for 5-6 hours at room temperature, layering, removing subnatant to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 1-10: 2, mixing, and stirring and reacting for 5-6 hours at the temperature of 60-80 ℃ and the rotating speed of 250-380 r/min to obtain a blank liquid; mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 3: 1-5: 1, adding a diluent which is 1-2 times of the mass of the blank liquid into a mixture of the blank liquid and a glutaraldehyde solution, and stirring and mixing for 20-60 min under the conditions that the temperature is 30-50 ℃ and the rotating speed is 300-360 r/min to obtain the environment-friendly paper oil-proofing agent. The environment-friendly paper oil-proof agent obtained by the invention has excellent oil-proof performance.

Description

Preparation method of environment-friendly paper oil-proof agent
Technical Field
The invention discloses a preparation method of an environment-friendly paper oil-proofing agent, belonging to the technical field of papermaking additives.
Background
With the development of economy and the improvement of living standard, people pay more and more attention to the safety, functionality and environmental friendliness of daily necessities. In the aspect of daily paper, the application field of oil-proof paper is more and more extensive, in particular to the aspect of food oil-proof packaging, the oil-proof paper not only has the function of resisting oil, but also requires that packaging materials can not cause food pollution and environmental pollution. The traditional method of imparting oil repellency to paper is to coat the paper with a plastic film. The paper-plastic packaging material is difficult to degrade in nature and easy to cause environmental pollution, and when the paper-plastic packaging material is in direct contact with food, pollutants remained in the paper-plastic packaging material can migrate to the food through the processes of absorption, dissolution, diffusion and the like, so that the paper-plastic packaging material causes certain harm to human health and environment. In recent years, a large amount of fluorine-containing polymer environment-friendly paper oil repellents have been used, and although the problems of degradation and recycling have been solved, perfluorooctanoic acid (PFOA) produced during the production process persists in the environment, has a biological storage property and is harmful to the human body, and it has not been possible to remove PFOA from fluorine-containing oil repellents. PFOA has been found in humans throughout the world, and canadian scientists have found that such oil repellents for food packaging can cause blood contamination.
Chitosan is a second most abundant substance in nature, second only to cellulose, and is prepared by deacetylation of chitin. The chitosan is biodegradable, nontoxic and pollution-free to the environment, and is widely applied to the fields of medicine environmental protection, spinning, paper making and the like at present. The compatibility and strong acting force between the chitosan and the cellulose lay a theoretical foundation for the application of the chitosan and the cellulose in the paper industry. The positive charge of the amino group in the chitosan under the acidic condition is combined with the negative charge of the fat or the lipid, so that the transfer of the fat or the lipid can be prevented, and the chitosan and the sodium alginate are compounded to paper for oil prevention, so that the effect which is the same as that of a fluorine oil-proof agent can be achieved. Researchers have prepared a coated oil-repellent agent for paper and a preparation method thereof, and the preparation method comprises the following steps: (1) mixing and stirring dialdehyde starch, oxidized starch and deionized water, heating to 90-95 ℃, and continuing stirring; (2) cooling to room temperature, adding polyvinylpyrrolidone, hydroxypropyl cellulose, sodium alginate and isolated soy protein, and stirring at the rotating speed of 400-500 r/min for 10-20 minutes; (3) adding chitosan and acetic acid, and stirring for 20-30 minutes at the rotating speed of 700-900 r/min; (4) heating to 80-90 ℃, adding coconut oil fatty acid diethanolamide, cinnamaldehyde and sodium citrate, stirring at the rotating speed of 600-800 r/min for 10-30 minutes, and cooling to room temperature to obtain the coconut oil fatty acid diethanolamide. The coated paper oil-proof agent can greatly improve the oil-proof performance and the strength performance of paper, has very excellent oil-proof effect and also has excellent water-proof effect. However, the conventional oil-repellent agents for paper still have a problem that the oil-repellent effect cannot be further improved, and therefore, research on the oil-repellent agents is needed.
Disclosure of Invention
The invention mainly solves the technical problems that: aiming at the problem that the oil-proof effect of the traditional paper oil-proof agent cannot be further improved, the preparation method of the environment-friendly paper oil-proof agent is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
(1) mixing allyl glycidyl ether and an organic solvent according to a mass ratio of 1: 8-1: 15, adding a chloroplatinic acid catalyst which is 0.2-0.3 times of the mass of the allyl glycidyl ether, stirring and mixing to obtain a mixed solution, and mixing the mixed solution with hydrogen-containing silicone oil according to a mass ratio of 5: 1-5: 2, mixing, reacting in a nitrogen atmosphere in a dark place, and then distilling under reduced pressure to obtain modified polysiloxane;
(2) mixing chitosan and acetic acid solution according to a mass ratio of 1: 10-1: 15, adding modified polysiloxane with the mass 2-4 times that of the chitosan, nano silicon dioxide with the mass 0.1-0.3 time that of the chitosan and a dispersing agent with the mass 0.02-0.04 time that of the chitosan, stirring for reaction, and performing rotary evaporation and concentration to obtain a concentrate;
(3) mixing the concentrate with toluene according to a mass ratio of 1: 2-1: 3, mixing, standing for layering, removing a lower layer liquid to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 1-10: 2, mixing, stirring and reacting to obtain a blank liquid;
(4) mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 3: 1-5: 1, adding a diluent with the mass 1-2 times that of the stock solution, stirring and mixing to obtain the environment-friendly paper oil-proofing agent.
The organic solvent in the step (1) is any one of toluene, xylene or benzene.
The modified polysiloxane mixture in the step (2) is prepared by mixing modified polysiloxane and isopropanol according to a mass ratio of 1: 5-1: 7, mixing to obtain a modified polysiloxane mixture.
The dispersant in the step (2) is any one of dispersant NNO, dispersant MF or dispersant 5040.
And (3) the isocyanate is any one of toluene diisocyanate or diphenylmethane diisocyanate.
And (4) the glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to the mass ratio of 1: 6-1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution.
The diluent in the step (4) is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent.
The silicon dioxide in the step (2) is prepared by mixing ethyl orthosilicate and ethanol solution according to a mass ratio of 1: 10-1: 15, adding ammonia water accounting for 0.2-0.4 time of the mass of the tetraethoxysilane and polyvinylpyrrolidone accounting for 0.1-0.3 time of the mass of the tetraethoxysilane, stirring for reaction, filtering, calcining to obtain pretreated nano silicon dioxide, mixing the pretreated nano silicon dioxide with 3-aminopropyltriethoxysilane according to the mass ratio of 2: 1-3: 1, adding anhydrous acetone which is 5-8 times of the mass of the pretreated nano-silica, stirring and mixing, and filtering to obtain a nano-silica blank, wherein the mass ratio of the nano-silica blank to potassium tetratitanate is 3: 1-5: 1, adding an ethanol solution which is 5-6 times of the mass of the nano silicon dioxide blank, carrying out microwave reaction, and filtering to obtain the nano silicon dioxide.
Microgel with the mass of 0.1-0.2 times that of the diluent can be added into the diluent in the step (4), and the microgel is prepared by weighing the following components in parts by weight: 100-120 parts of polyvinyl alcohol, 60-80 parts of gelatin, 300-450 parts of water, 30-50 parts of glutaraldehyde aqueous solution and 10-30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, vacuum drying, crushing, and sieving to obtain the microgel.
The invention has the beneficial effects that:
(1) the invention uses modified polysiloxane to process chitosan when preparing environment-friendly paper oil-proof agent, and adds nano-silicon dioxide in the processing process, firstly, polysiloxane forms epoxy group on polysiloxane molecular chain after being modified, epoxy group ring-opening can react with amino and hydroxyl on chitosan molecule after being mixed and reacted with chitosan, and crosslinking degree of product after film forming is improved, thereby improving density of product after film forming, and due to hydrophobic property of polysiloxane, hydrophobicity of product is improved at the same time, secondly, nano-silicon dioxide is added in the processing process, on one hand, nano-silicon dioxide has hydrophilic and oleophobic property, and oil-proof property of product is improved after being added in product, on the other hand, part of hydroxyl on surface of silicon dioxide can react with epoxy group on modified polysiloxane, therefore, the nano silicon dioxide is fixed in the product, so that the hydrophilicity of the surface of the silicon dioxide is reduced, the residual hydroxyl groups on the surface of the silicon dioxide are combined with each other through hydrogen bonds, isolated hydrogen atoms have strong electropositivity and are easy to adsorb with electronegative atoms, so that the transfer of fat or lipid can be prevented, the oil resistance of the product is improved, and meanwhile, the density of the product can be further improved due to the addition of the silicon dioxide, so that the oil resistance of the product is further improved;
(2) the nano silicon dioxide added in the preparation of the environment-friendly paper oil repellent agent is self-made nano silicon dioxide, the addition of the nano silicon dioxide can be matched with modified polysiloxane to improve the oil repellency of a product, the self-made nano silicon dioxide is of a porous structure, the interior of pores and the surface of the silicon dioxide both contain a lamellar structure of potassium tetratitanate, and the potassium tetratitanate has good hydrophilicity, so that the oleophobic property of the product can be improved after the nano silicon dioxide is added into the product, and the pore structure of the nano silicon dioxide is complicated after the potassium tetratitanate enters the pore structure of the nano silicon dioxide, so that the product has good oleophobic property and also has certain waterproof property.
Detailed Description
Mixing allyl glycidyl ether and an organic solvent according to a mass ratio of 1: 8-1: 15, adding a chloroplatinic acid catalyst which is 0.2-0.3 times of the mass of the allyl glycidyl ether into a beaker, stirring and mixing for 30-50 min at the temperature of 30-45 ℃ and the rotating speed of 300-350 r/min to obtain a mixed solution, and mixing the mixed solution with hydrogen-containing silicone oil according to the mass ratio of 5: 1-5: 2, mixing the mixture in a three-neck flask, controlling the adding rate of hydrogen-containing silicone oil to be 5-6 mL/min, introducing nitrogen into the three-neck flask at the rate of 20-30 mL/min, reacting for 5-6 h in a dark place at the temperature of 80-90 ℃ and the rotating speed of 280-350 r/min to obtain a modified polysiloxane mixture, and distilling the modified polysiloxane mixture at the temperature of 120-130 ℃ under reduced pressure for 2-3 h to obtain modified polysiloxane; mixing chitosan and an acetic acid solution with the mass fraction of 2-4% according to the mass ratio of 1: 10-1: 15, mixing the mixture in a flask, adding modified polysiloxane with the mass 2-4 times that of chitosan, nano silicon dioxide with the mass 0.1-0.3 time that of chitosan and a dispersing agent with the mass 0.02-0.04 time that of chitosan into the flask, stirring and reacting for 3-5 hours at the temperature of 60-65 ℃ and the rotating speed of 250-350 r/min, transferring the materials in the flask into a rotary evaporator, and performing rotary evaporation and concentration for 2-6 hours under the conditions of the temperature of 100-120 ℃, the rotating speed of 120-150 r/min and the pressure of 500-600 kPa to obtain a concentrate; mixing the concentrate with toluene according to a mass ratio of 1: 2-1: 3, mixing, standing for 5-6 hours at room temperature, layering, removing subnatant to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 1-10: 2, mixing, and stirring and reacting for 5-6 hours at the temperature of 60-80 ℃ and the rotating speed of 250-380 r/min to obtain a blank liquid; mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 3: 1-5: 1, adding a diluent which is 1-2 times of the mass of the blank liquid into a mixture of the blank liquid and a glutaraldehyde solution, and stirring and mixing for 20-60 min under the conditions that the temperature is 30-50 ℃ and the rotating speed is 300-360 r/min to obtain the environment-friendly paper oil-proofing agent. The organic solvent is any one of toluene, xylene or benzene. The modified polysiloxane mixture is prepared by mixing modified polysiloxane and isopropanol according to a mass ratio of 1: 5-1: 7, mixing to obtain a modified polysiloxane mixture. The dispersant is any one of dispersant NNO, dispersant MF or dispersant 5040. The isocyanate is any one of toluene diisocyanate or diphenylmethane diisocyanate. The glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to a mass ratio of 1: 6-1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution. The diluent is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent. The nano silicon dioxide is prepared by mixing ethyl orthosilicate and ethanol solution according to a mass ratio of 1: 10-1: 15, adding ammonia water accounting for 0.2-0.4 time of the mass of the tetraethoxysilane and polyvinylpyrrolidone accounting for 0.1-0.3 time of the mass of the tetraethoxysilane, stirring for reaction, filtering, calcining to obtain pretreated nano silicon dioxide, mixing the pretreated nano silicon dioxide with 3-aminopropyltriethoxysilane according to the mass ratio of 2: 1-3: 1, adding anhydrous acetone which is 5-8 times of the mass of the pretreated nano-silica, stirring and mixing, and filtering to obtain a nano-silica blank, wherein the mass ratio of the nano-silica blank to potassium tetratitanate is 3: 1-5: 1, adding an ethanol solution which is 5-6 times of the mass of the nano silicon dioxide blank, carrying out microwave reaction, and filtering to obtain the nano silicon dioxide. The microgel with the mass 0.1-0.2 times that of the diluent can be added into the diluent, and the microgel is prepared by weighing the following components in parts by weight: 100-120 parts of polyvinyl alcohol, 60-80 parts of gelatin, 300-450 parts of water, 30-50 parts of glutaraldehyde aqueous solution and 10-30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, vacuum drying, crushing, and sieving to obtain the microgel.
Example 1
Mixing allyl glycidyl ether and an organic solvent according to a mass ratio of 1: 15, adding chloroplatinic acid catalyst with the mass 0.3 time that of the allyl glycidyl ether into a beaker, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 350r/min to obtain a mixed solution, and mixing the mixed solution with hydrogen-containing silicone oil according to the mass ratio of 5: 2, mixing the mixture in a three-neck flask, controlling the adding rate of hydrogen-containing silicone oil to be 6mL/min, introducing nitrogen into the three-neck flask at the rate of 30mL/min, reacting for 6 hours in a dark place at the temperature of 90 ℃ and the rotating speed of 350r/min to obtain a modified polysiloxane mixture, and distilling the modified polysiloxane mixture at the temperature of 130 ℃ under reduced pressure for 3 hours to obtain modified polysiloxane; mixing chitosan and an acetic acid solution with the mass fraction of 4% according to the mass ratio of 1: 15, mixing the mixture in a flask, adding modified polysiloxane with the mass being 4 times that of chitosan, nano silicon dioxide with the mass being 0.3 time that of chitosan and a dispersing agent with the mass being 0.04 time that of chitosan into the flask, stirring and reacting for 5 hours at the temperature of 65 ℃ and the rotating speed of 350r/min, transferring the materials in the flask into a rotary evaporator, and carrying out rotary evaporation and concentration for 6 hours at the temperature of 120 ℃, the rotating speed of 150r/min and the pressure of 600kPa to obtain a concentrate; mixing the concentrate with toluene according to a mass ratio of 1: 3, mixing, standing for 6 hours at room temperature, layering, removing subnatant to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 2, mixing, stirring and reacting for 6 hours at the temperature of 80 ℃ and the rotating speed of 380r/min to obtain blank liquid; mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 5: 1, adding a diluent which is 2 times of the mass of the blank liquid into the mixture of the blank liquid and the glutaraldehyde solution, and stirring and mixing for 60min under the conditions that the temperature is 50 ℃ and the rotating speed is 360r/min to obtain the environment-friendly paper oil-proofing agent. The organic solvent is toluene. The modified polysiloxane mixture is prepared by mixing modified polysiloxane and isopropanol according to a mass ratio of 1: 7, mixing to obtain a modified polysiloxane mixture. The dispersant is dispersant NNO. The isocyanate is toluene diisocyanate. The glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to a mass ratio of 1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution. The diluent is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent.
Example 2
Mixing chitosan and an acetic acid solution with the mass fraction of 4% according to the mass ratio of 1: 15, adding polydimethylsiloxane 4 times the mass of chitosan, nano silicon dioxide 0.3 times the mass of chitosan and a dispersing agent 0.04 times the mass of chitosan into a flask, stirring and reacting for 5 hours at the temperature of 65 ℃ and the rotating speed of 350r/min, transferring the materials in the flask into a rotary evaporator, and carrying out rotary evaporation and concentration for 6 hours at the temperature of 120 ℃, the rotating speed of 150r/min and the pressure of 600kPa to obtain a concentrate; mixing the concentrate with toluene according to a mass ratio of 1: 3, mixing, standing for 6 hours at room temperature, layering, removing subnatant to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 2, mixing, stirring and reacting for 6 hours at the temperature of 80 ℃ and the rotating speed of 380r/min to obtain blank liquid; mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 5: 1, adding a diluent which is 2 times of the mass of the blank liquid into the mixture of the blank liquid and the glutaraldehyde solution, and stirring and mixing for 60min under the conditions that the temperature is 50 ℃ and the rotating speed is 360r/min to obtain the environment-friendly paper oil-proofing agent. The organic solvent is toluene. The dispersant is dispersant NNO. The isocyanate is toluene diisocyanate. The glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to a mass ratio of 1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution. The diluent is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent. The nano silicon dioxide is prepared by mixing ethyl orthosilicate and ethanol solution according to a mass ratio of 1: 15, adding ammonia water with the mass of 0.4 time of that of the tetraethoxysilane and polyvinylpyrrolidone with the mass of 0.3 time of that of the tetraethoxysilane, stirring for reaction, filtering and calcining to obtain pretreated nano silicon dioxide, mixing the pretreated nano silicon dioxide with 3-aminopropyltriethoxysilane according to the mass ratio of 3: 1, adding anhydrous acetone with the mass 8 times that of the pretreated nano-silica, stirring and mixing, and filtering to obtain a nano-silica blank, wherein the mass ratio of the nano-silica blank to potassium tetratitanate is 5: 1, adding ethanol solution with the mass 6 times of that of the nano silicon dioxide blank, carrying out microwave reaction, and filtering to obtain the nano silicon dioxide. Microgel with the mass of 0.2 times of that of the diluent can be added into the diluent, and the microgel is prepared by weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution and 30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, vacuum drying, crushing and sieving to obtain the microgel.
Example 3
Mixing allyl glycidyl ether and an organic solvent according to a mass ratio of 1: 15, adding chloroplatinic acid catalyst with the mass 0.3 time that of the allyl glycidyl ether into a beaker, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 350r/min to obtain a mixed solution, and mixing the mixed solution with hydrogen-containing silicone oil according to the mass ratio of 5: 2, mixing the mixture in a three-neck flask, controlling the adding rate of hydrogen-containing silicone oil to be 6mL/min, introducing nitrogen into the three-neck flask at the rate of 30mL/min, reacting for 6 hours in a dark place at the temperature of 90 ℃ and the rotating speed of 350r/min to obtain a modified polysiloxane mixture, and distilling the modified polysiloxane mixture at the temperature of 130 ℃ under reduced pressure for 3 hours to obtain modified polysiloxane; mixing chitosan and an acetic acid solution with the mass fraction of 4% according to the mass ratio of 1: 15, mixing the mixture in a flask, adding modified polysiloxane with the mass being 4 times that of the chitosan and a dispersant with the mass being 0.04 time that of the chitosan into the flask, stirring and reacting for 5 hours at the temperature of 65 ℃ and the rotation speed of 350r/min, transferring the materials in the flask into a rotary evaporator, and performing rotary evaporation and concentration for 6 hours at the temperature of 120 ℃, the rotation speed of 150r/min and the pressure of 600kPa to obtain a concentrate; mixing the concentrate with toluene according to a mass ratio of 1: 3, mixing, standing for 6 hours at room temperature, layering, removing subnatant to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 2, mixing, stirring and reacting for 6 hours at the temperature of 80 ℃ and the rotating speed of 380r/min to obtain blank liquid; mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 5: 1, adding a diluent which is 2 times of the mass of the blank liquid into the mixture of the blank liquid and the glutaraldehyde solution, and stirring and mixing for 60min under the conditions that the temperature is 50 ℃ and the rotating speed is 360r/min to obtain the environment-friendly paper oil-proofing agent. The organic solvent is toluene. The modified polysiloxane mixture is prepared by mixing modified polysiloxane and isopropanol according to a mass ratio of 1: 7, mixing to obtain a modified polysiloxane mixture. The dispersant is dispersant NNO. The isocyanate is toluene diisocyanate. The glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to a mass ratio of 1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution. The diluent is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent. The nano silicon dioxide is prepared by mixing ethyl orthosilicate and ethanol solution according to a mass ratio of 1: 15, adding ammonia water with the mass of 0.4 time of that of the tetraethoxysilane and polyvinylpyrrolidone with the mass of 0.3 time of that of the tetraethoxysilane, stirring for reaction, filtering and calcining to obtain pretreated nano silicon dioxide, mixing the pretreated nano silicon dioxide with 3-aminopropyltriethoxysilane according to the mass ratio of 3: 1, adding anhydrous acetone with the mass 8 times that of the pretreated nano-silica, stirring and mixing, and filtering to obtain a nano-silica blank, wherein the mass ratio of the nano-silica blank to potassium tetratitanate is 5: 1, adding ethanol solution with the mass 6 times of that of the nano silicon dioxide blank, carrying out microwave reaction, and filtering to obtain the nano silicon dioxide. Microgel with the mass of 0.2 times of that of the diluent can be added into the diluent, and the microgel is prepared by weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution and 30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, vacuum drying, crushing and sieving to obtain the microgel.
Example 4
Mixing allyl glycidyl ether and an organic solvent according to a mass ratio of 1: 15, adding chloroplatinic acid catalyst with the mass 0.3 time that of the allyl glycidyl ether into a beaker, stirring and mixing for 50min at the temperature of 45 ℃ and the rotating speed of 350r/min to obtain a mixed solution, and mixing the mixed solution with hydrogen-containing silicone oil according to the mass ratio of 5: 2, mixing the mixture in a three-neck flask, controlling the adding rate of hydrogen-containing silicone oil to be 6mL/min, introducing nitrogen into the three-neck flask at the rate of 30mL/min, reacting for 6 hours in a dark place at the temperature of 90 ℃ and the rotating speed of 350r/min to obtain a modified polysiloxane mixture, and distilling the modified polysiloxane mixture at the temperature of 130 ℃ under reduced pressure for 3 hours to obtain modified polysiloxane; mixing chitosan and an acetic acid solution with the mass fraction of 4% according to the mass ratio of 1: 15, mixing the mixture in a flask, adding modified polysiloxane with the mass being 4 times that of chitosan, nano silicon dioxide with the mass being 0.3 time that of chitosan and a dispersing agent with the mass being 0.04 time that of chitosan into the flask, stirring and reacting for 5 hours at the temperature of 65 ℃ and the rotating speed of 350r/min, transferring the materials in the flask into a rotary evaporator, and carrying out rotary evaporation and concentration for 6 hours at the temperature of 120 ℃, the rotating speed of 150r/min and the pressure of 600kPa to obtain a concentrate; mixing the concentrate with toluene according to a mass ratio of 1: 3, mixing, standing for 6 hours at room temperature, layering, and removing subnatant to obtain a pretreatment concentrate; mixing the pretreatment concentrate with a glutaraldehyde solution according to a mass ratio of 5: 1, adding a diluent which is 2 times of the mass of the blank liquid into the mixture of the blank liquid and the glutaraldehyde solution, and stirring and mixing for 60min under the conditions that the temperature is 50 ℃ and the rotating speed is 360r/min to obtain the environment-friendly paper oil-proofing agent. The organic solvent is toluene. The modified polysiloxane mixture is prepared by mixing modified polysiloxane and isopropanol according to a mass ratio of 1: 7, mixing to obtain a modified polysiloxane mixture. The dispersant is dispersant NNO. The glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to a mass ratio of 1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution. The diluent is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent. The nano silicon dioxide is prepared by mixing ethyl orthosilicate and ethanol solution according to a mass ratio of 1: 15, adding ammonia water with the mass of 0.4 time of that of the tetraethoxysilane and polyvinylpyrrolidone with the mass of 0.3 time of that of the tetraethoxysilane, stirring for reaction, filtering and calcining to obtain pretreated nano silicon dioxide, mixing the pretreated nano silicon dioxide with 3-aminopropyltriethoxysilane according to the mass ratio of 3: 1, adding anhydrous acetone with the mass 8 times that of the pretreated nano-silica, stirring and mixing, and filtering to obtain a nano-silica blank, wherein the mass ratio of the nano-silica blank to potassium tetratitanate is 5: 1, adding ethanol solution with the mass 6 times of that of the nano silicon dioxide blank, carrying out microwave reaction, and filtering to obtain the nano silicon dioxide. Microgel with the mass of 0.2 times of that of the diluent can be added into the diluent, and the microgel is prepared by weighing the following components in parts by weight: 120 parts of polyvinyl alcohol, 80 parts of gelatin, 450 parts of water, 50 parts of glutaraldehyde aqueous solution and 30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, vacuum drying, crushing and sieving to obtain the microgel.
The environment-friendly paper oil-repellent agents obtained in examples 1 to 4 were subjected to performance testing by the following specific testing method:
the contact angle of the liquid paraffin on the surface of the paper sample is measured by a DAT1122 type contact angle measuring instrument, the measuring temperature is (25 +/-2) DEG C, and the relative humidity is (65 +/-2)%. Specific detection results are shown in table 1:
table 1: performance test meter
Detecting content Example 1 Example 2 Example 3 Example 4
Contact Angle/° 120 95 101 98
As can be seen from the detection results in Table 1, the environment-friendly paper oil repellent agent obtained by the invention has excellent oil-proof performance.

Claims (9)

1. A preparation method of an environment-friendly paper oil-proofing agent is characterized by comprising the following steps:
(1) mixing allyl glycidyl ether and an organic solvent according to a mass ratio of 1: 8-1: 15, adding a chloroplatinic acid catalyst which is 0.2-0.3 times of the mass of the allyl glycidyl ether, stirring and mixing to obtain a mixed solution, and mixing the mixed solution with hydrogen-containing silicone oil according to a mass ratio of 5: 1-5: 2, mixing, reacting in a nitrogen atmosphere in a dark place, and then distilling under reduced pressure to obtain modified polysiloxane;
(2) mixing chitosan and acetic acid solution according to a mass ratio of 1: 10-1: 15, adding modified polysiloxane with the mass 2-4 times that of the chitosan, nano silicon dioxide with the mass 0.1-0.3 time that of the chitosan and a dispersing agent with the mass 0.02-0.04 time that of the chitosan, stirring for reaction, and performing rotary evaporation and concentration to obtain a concentrate;
(3) mixing the concentrate with toluene according to a mass ratio of 1: 2-1: 3, mixing, standing for layering, removing a lower layer liquid to obtain a pretreatment concentrate, and mixing the pretreatment concentrate with isocyanate according to a mass ratio of 10: 1-10: 2, mixing, stirring and reacting to obtain a blank liquid;
(4) mixing the blank liquid and the glutaraldehyde solution according to the mass ratio of 3: 1-5: 1, adding a diluent with the mass 1-2 times that of the stock solution, stirring and mixing to obtain the environment-friendly paper oil-proofing agent.
2. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: the organic solvent in the step (1) is any one of toluene, xylene or benzene.
3. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: the modified polysiloxane mixture in the step (2) is prepared by mixing modified polysiloxane and isopropanol according to a mass ratio of 1: 5-1: 7, mixing to obtain a modified polysiloxane mixture.
4. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: the dispersant in the step (2) is any one of dispersant NNO, dispersant MF or dispersant 5040.
5. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: and (3) the isocyanate is any one of toluene diisocyanate or diphenylmethane diisocyanate.
6. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: and (4) the glutaraldehyde solution is prepared by mixing glutaraldehyde and diethyl ether according to the mass ratio of 1: 6-1: 8, mixing, stirring and dispersing to obtain a glutaraldehyde solution.
7. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: the diluent in the step (4) is prepared by mixing n-butanol and ethanol according to a mass ratio of 4: 1, mixing to obtain the diluent.
8. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: the nano silicon dioxide in the step (2) is prepared by mixing ethyl orthosilicate and ethanol solution according to a mass ratio of 1: 10-1: 15, adding ammonia water accounting for 0.2-0.4 time of the mass of the tetraethoxysilane and polyvinylpyrrolidone accounting for 0.1-0.3 time of the mass of the tetraethoxysilane, stirring for reaction, filtering, calcining to obtain pretreated nano silicon dioxide, mixing the pretreated nano silicon dioxide with 3-aminopropyltriethoxysilane according to the mass ratio of 2: 1-3: 1, adding anhydrous acetone which is 5-8 times of the mass of the pretreated nano-silica, stirring and mixing, and filtering to obtain a nano-silica blank, wherein the mass ratio of the nano-silica blank to potassium tetratitanate is 3: 1-5: 1, adding an ethanol solution which is 5-6 times of the mass of the nano silicon dioxide blank, carrying out microwave reaction, and filtering to obtain the nano silicon dioxide.
9. The method for preparing the environment-friendly oil-repellent agent for paper as claimed in claim 1, wherein: microgel with the mass of 0.1-0.2 times that of the diluent can be added into the diluent in the step (4), and the microgel is prepared by weighing the following components in parts by weight: 100-120 parts of polyvinyl alcohol, 60-80 parts of gelatin, 300-450 parts of water, 30-50 parts of glutaraldehyde aqueous solution and 10-30 parts of hydrochloric acid, mixing the polyvinyl alcohol with the water, heating and stirring to obtain a polyvinyl alcohol solution, cooling the polyvinyl alcohol solution, mixing the cooled polyvinyl alcohol solution with the gelatin, sequentially adding the hydrochloric acid and the glutaraldehyde aqueous solution, stirring and mixing, filtering, cutting into blocks, washing, vacuum drying, crushing, and sieving to obtain the microgel.
CN201911063209.1A 2019-11-04 2019-11-04 Preparation method of environment-friendly paper oil-proof agent Pending CN110685185A (en)

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