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CN-122011427-A - Lignocellulose hydrophobic oil-resistant agent, preparation method and application

CN122011427ACN 122011427 ACN122011427 ACN 122011427ACN-122011427-A

Abstract

The invention discloses a lignocellulose hydrophobic oil-resistant agent, a preparation method and application thereof, and belongs to the technical field of oil-resistant agent preparation. The preparation method of the lignocellulose hydrophobic oil-resistant agent comprises the steps of constructing a ternary eutectic solvent by adopting a hydrogen bond acceptor, a Bronsted acid donor and Lewis acid metal salt, synergistically cracking a lignin network in a machine pulp, providing a catalytic environment, synchronously adding the machine pulp and a biological base modifier, namely coumaric acid-plant sterol ester, in the solvent, integrally completing in-situ nanocrystallization of fibers and surface hydrophobic esterification functionalization under an inert atmosphere, and obtaining the lignocellulose hydrophobic oil-resistant agent by shearing and dispersing, centrifugal purification and reduced pressure distillation of a reaction mixture assisted by dihydro levoglucosone. According to the invention, the synchronous construction of efficient nanocrystallization dissociation of the chemimechanical pulp and the modified catalytic environment is realized through the ternary eutectic solvent, so that the integrated process of nanocrystallization-hydrophobic oil resistance modification is realized, toxic and harmful substances are avoided, and the method is environment-friendly.

Inventors

  • LI PEIYI
  • LIU RUILIN
  • XUE WENJING
  • SUN BOLONG

Assignees

  • 陕西科技大学

Dates

Publication Date
20260512
Application Date
20260203

Claims (10)

  1. 1. The preparation method of the lignocellulose hydrophobic oil-resistant agent is characterized by comprising the following steps of: Mixing a hydrogen bond acceptor, a Bronsted acid donor and Lewis acid metal salt according to a preset molar ratio, and heating to obtain a ternary eutectic solvent; Adding chemimechanical pulp and coumaric acid-plant sterol ester into the ternary eutectic solvent, and reacting under the protection of inert gas and stirring to obtain a reaction mixture; mixing the reaction mixture with dihydro-L-glucosone, performing high-speed shearing and centrifugation treatment to obtain a primary dispersion, extracting supernatant in the primary dispersion, and performing reduced pressure distillation to obtain the lignocellulose hydrophobic oil-resistant agent.
  2. 2. The preparation method of the lignocellulose hydrophobic oil-resistant agent is characterized in that a hydrogen bond acceptor is betaine, a Bronsted acid donor is p-toluenesulfonic acid, a Lewis acid metal salt is ferric trichloride, and a preset molar ratio is 1 (0.8-1.2) to 0.3-0.7.
  3. 3. The preparation method of the lignocellulose hydrophobic oil-resistant agent according to claim 1 is characterized in that the mass ratio of the chemical-mechanical pulp to the ternary eutectic solvent is 1:10-1:40, and the weight of the coumaric acid-plant sterol ester added into the ternary eutectic solvent is 10% -40% of the dry weight of the chemical-mechanical pulp added into the ternary eutectic solvent.
  4. 4. The preparation method of the lignocellulose hydrophobic oil-repellent agent according to claim 1, wherein the inert gas in the reaction is nitrogen or argon under the protection of the inert gas and under the stirring condition, the speed of the stirring condition is 300-1500 rpm, the reaction time is 2-5 hours, and the reaction temperature is 90-120 ℃.
  5. 5. The preparation method of the lignocellulose hydrophobic oil-repellent agent according to claim 1, wherein the solid content of the lignocellulose hydrophobic oil-repellent agent is 1% -5%.
  6. 6. The preparation method of the lignocellulose hydrophobic oil-repellent agent according to claim 1, which is characterized in that coumaric acid-plant sterol ester is synthesized in advance by an enzyme catalytic esterification method, and specifically comprises the following steps: Mixing coumaric acid and plant sterol, adding a biocatalyst and a molecular sieve accounting for 5% -10% of the total weight of the coumaric acid and the plant sterol, reacting for 24-72 hours in a tert-amyl alcohol solvent at 50-60 ℃, and sequentially evaporating, filtering, cooling and crystallizing to obtain coumaric acid-plant sterol ester.
  7. 7. The method for preparing a lignocellulose hydrophobic oil repellent agent according to claim 6, wherein the biocatalyst is an acid-resistant whole-cell catalyst.
  8. 8. The preparation method of the lignocellulose hydrophobic oil-repellent agent according to claim 1, wherein the volume ratio of the reaction mixture to the dihydro-l-glucosone is 1 (2-5), and the rotational speed of the centrifugal treatment is 8000-12000 rpm.
  9. 9. A lignocellulose hydrophobic oil repellent agent, which is characterized by being prepared by the preparation method of the lignocellulose hydrophobic oil repellent agent according to any one of claims 1-8.
  10. 10. Use of the lignocellulosic hydrophobic oil repellent according to claim 9 for the preparation of environmental packaging coatings, waterproof textiles, polymer reinforced composites or 3D printing photocurable resin compositions.

Description

Lignocellulose hydrophobic oil-resistant agent, preparation method and application Technical Field The invention relates to the technical field of preparation of oil-resistant agents, in particular to a lignocellulose hydrophobic oil-resistant agent, a preparation method and application thereof. Background The nanocellulose has excellent characteristics of being renewable, biodegradable, high specific strength and the like, and has great potential in the fields of packaging, coating and composite materials. However, the abundant hydroxyl groups on the surface of the polymer make the polymer hydrophilic, which limits the application in the waterproof and oil-resistant fields. The prior art generally adopts a two-step method of preparing nano cellulose and then carrying out surface hydrophobic modification, has long process flow and high energy consumption, and usually uses fluorine-containing compounds or toxic silane, and does not accord with the green chemical trend. The chemi-mechanical pulp is an ideal raw material for preparing nanocellulose with high yield and low cost, but the high lignin content of the chemi-mechanical pulp is challenging to the traditional nanocrystallization method. The eutectic solvent is taken as a novel green solvent, and shows unique advantages in the aspect of biomass pretreatment, but the prior art is mostly concentrated on component dissociation rather than functional integration, and the prior eutectic solvent is mostly a binary system, so that the nano dissociation effect on raw materials with high lignin content such as chemi-mechanical pulp is limited, and the catalytic environment required by modification reaction cannot be synchronously provided. Therefore, how to realize efficient nanocrystallization of chemi-mechanical pulp has become a technical problem to be overcome by those skilled in the art. Disclosure of Invention The invention aims to provide a lignocellulose water-repellent and oil-repellent agent, a preparation method and application thereof, so as to solve the problems that the nanocrystallization efficiency of chemical pulp is low and high-efficiency utilization is difficult to realize in the prior art. The invention solves the technical problems by the following technical proposal: the invention provides a preparation method of a lignocellulose hydrophobic oil-repellent agent, which comprises the following steps: Mixing a hydrogen bond acceptor, a Bronsted acid donor and Lewis acid metal salt according to a preset molar ratio, and heating to obtain a ternary eutectic solvent; Adding chemimechanical pulp and coumaric acid-plant sterol ester into the ternary eutectic solvent, and reacting under the protection of inert gas and stirring to obtain a reaction mixture; mixing the reaction mixture with dihydro-L-glucosone, performing high-speed shearing and centrifugation treatment to obtain a primary dispersion, extracting supernatant in the primary dispersion, and performing reduced pressure distillation to obtain the lignocellulose hydrophobic oil-resistant agent. The invention is further improved in that the hydrogen bond acceptor is betaine, the Bronsted acid donor is p-toluenesulfonic acid, the Lewis acid metal salt is ferric trichloride, and the specific molar ratio is 1 (0.8-1.2) to 0.3-0.7. The invention is further improved in that the mass ratio of the chemical mechanical pulp to the ternary eutectic solvent is 1:10-1:40, and the weight of the coumaric acid-plant sterol ester added into the ternary eutectic solvent is 10% -40% of the dry weight of the chemical mechanical pulp added into the ternary eutectic solvent. The invention is further improved in that the inert gas in the reaction is nitrogen or argon under the protection of the inert gas and under the stirring condition, the speed of the stirring condition is 300-1500 rpm, the reaction time is 2-5 hours, and the reaction temperature is 90-120 ℃. The invention is further improved in that the solid content of the lignocellulose hydrophobic oil-repellent agent is 1% -5%. The invention further improves that coumaric acid-plant sterol ester is synthesized in advance by an enzyme catalytic esterification method, and specifically comprises the following steps: Mixing coumaric acid and plant sterol, adding a biocatalyst and a molecular sieve accounting for 5% -10% of the total weight of the coumaric acid and the plant sterol, reacting for 24-72 hours in a tert-amyl alcohol solvent at 50-60 ℃, and sequentially evaporating, filtering, cooling and crystallizing to obtain coumaric acid-plant sterol ester. The invention is further improved in that the biocatalyst is an acid-resistant whole cell catalyst. The invention is further improved in that the volume ratio of the reaction mixture to the dihydro-L-glucosone is 1 (2-5), and the rotational speed of centrifugal treatment is 8000-12000 rpm. The invention provides a lignocellulose hydrophobic oil-resistant agent, which is prepared by adopting the preparation