CN111333816A - Cationic emulsifying dispersant for rosin size and preparation method thereof - Google Patents

Cationic emulsifying dispersant for rosin size and preparation method thereof Download PDF

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CN111333816A
CN111333816A CN202010160110.XA CN202010160110A CN111333816A CN 111333816 A CN111333816 A CN 111333816A CN 202010160110 A CN202010160110 A CN 202010160110A CN 111333816 A CN111333816 A CN 111333816A
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rosin size
emulsifying dispersant
cationic emulsifying
cationic
mixture
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卢志勇
栾星星
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Zhejiang Best Chemical Co ltd
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
    • 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
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • 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
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • D21H17/24—Polysaccharides
    • 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
    • D21H17/24—Polysaccharides
    • D21H17/30—Alginic acid or alginates
    • 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
    • D21H17/52—Epoxy resins
    • 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
    • D21H17/53—Polyethers; Polyesters
    • 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
    • D21H17/62—Rosin; 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paper (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The invention provides a cationic emulsifying dispersant for rosin size and a preparation method thereof. The preparation method of the cationic emulsifying dispersant for the rosin size comprises the following steps: s100, adipic acid, N-dimethyl-1, 3-propane diamine and epoxy chloropropane are used as raw materials, and a cationic emulsifying dispersant for rosin size is obtained through condensation reaction and addition ring-opening reaction. The cationic emulsifying dispersant for rosin size obtained by the invention has the advantages of low cost, stable property and excellent dispersing performance.

Description

Cationic emulsifying dispersant for rosin size and preparation method thereof
Technical Field
The invention relates to the field of manufacturing of papermaking chemicals, in particular to a cationic emulsifying dispersant for rosin size and a preparation method thereof.
Background
Rosin size is a traditional sizing agent widely used in the papermaking industry, and includes four types of saponified rosin size, strengthened rosin size, anion dispersed rosin size, cation dispersed rosin size and the like.
The cation dispersed rosin size is an electropositive dispersed sizing agent, has stronger electrostatic attraction with the negative charge of paper pulp fibers, can be automatically remained on the fibers, embodies excellent impurity interference resistance, is suitable for occasions where a large amount of secondary fibers exist, can reduce the using amount of aluminum sulfate in the sizing process, realizes neutral or near-neutral sizing, can resist calcium carbonate filler, has reduced corrosion to papermaking equipment, and gradually becomes a main sizing agent of a papermaking system with high neutral papermaking and white water circulation.
The dispersing emulsifier used for cationic dispersion rosin size in the market at present is mainly polyamide epichlorohydrin (PAE), polyamide is usually obtained by high-temperature polycondensation of adipic acid and diethylenetriamine, and then crosslinking is carried out through epoxy chloropropane, so that the use amount of diethylenetriamine needs to be increased in order to avoid gelation in the polycondensation stage, excessive epichlorohydrin needs to be used in order to avoid gelation in the crosslinking stage, the content of free epichlorohydrin and epichlorohydrin in the obtained emulsifier is increased, and the cationic density in the emulsifier molecule is reduced, and the quality of the rosin size and finished paper is directly influenced. In addition, diethylenetriamine is expensive and the production cost is high.
In order to further promote the application of cation dispersed rosin size in the papermaking industry, the development of a cation emulsifying dispersant with excellent performance and low cost is urgently needed in the field.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems.
Therefore, the first purpose of the invention is to provide a preparation method of the cationic emulsifying dispersant for rosin size.
The second purpose of the invention is to provide a cationic emulsifying dispersant for rosin size.
In order to achieve the first object of the present invention, an embodiment of the present invention provides a preparation method of a cationic emulsifying dispersant for rosin size, comprising the steps of: s100, adipic acid, N-dimethyl-1, 3-propane diamine and epoxy chloropropane are used as raw materials, and a cationic emulsifying dispersant for rosin size is obtained through condensation reaction and addition ring-opening reaction.
In addition, the technical solution provided by the above embodiment of the present invention may further have the following additional technical features:
in the above technical solution, the step S100 specifically includes the following steps:
s1, carrying out condensation reaction by adopting a mixture of adipic acid and N, N-dimethyl-1, 3-propane diamine to obtain N1, N6-bis (3-dimethylaminopropyl) adipamide;
Figure BDA0002405257460000021
s2, performing heating reaction on the N1, N6-bis (3-dimethylaminopropyl) adipamide obtained in the step S1 and the epichlorohydrin to obtain a dication intermediate;
Figure BDA0002405257460000022
s3, carrying out addition ring-opening reaction by adopting the mixture of the N, N-dimethyl-1, 3-propane diamine and the dicationic intermediate obtained in the step S2 to obtain cationic polyamine;
Figure BDA0002405257460000031
and S4, performing heating reaction on the epoxy chloropropane and the cationic polyamine obtained in the step S3 to obtain the cationic emulsifying dispersant for the rosin size.
Figure BDA0002405257460000032
In any of the above technical solutions, the step S100 specifically includes the following steps:
step S102, according to adipic acid: n, N-dimethyl-1, 3-propanediamine ═ 1.8 to 2.2: 1, uniformly mixing the adipic acid and the N, N-dimethyl-1, 3-propane diamine in water, heating for dehydration, heating for condensation, cooling and adding water for dilution to obtain N1, N6-bis (3-dimethylaminopropyl) adipamide;
step S104, adding N1, N6-bis (3-dimethylaminopropyl) adipamide: epichlorohydrin 2: (0.8-1.2), uniformly mixing the N1, N6-bis (3-dimethylaminopropyl) adipamide obtained in the step S102 and the epichlorohydrin, heating for reaction, cooling, and obtaining a dicationic intermediate;
step S106, according to the weight ratio of N, N-dimethyl-1, 3-propane diamine: dicationic intermediate ═ 2: (0.8-1.2) a molar ratio of the N, N-dimethyl-1, 3-propanediamine and the dicationic intermediate obtained by the step S104 to be uniformly mixed and subjected to an addition ring-opening reaction to obtain a cationic polyamine;
step S108, according to the epoxy chloropropane: cationic polyamine ═ 2: (0.8-1.2), uniformly mixing the epichlorohydrin with the cationic polyamine obtained in the step S106, heating to react, cooling, adding water to adjust the solid content, and obtaining the cationic emulsifying dispersant for rosin size.
In any of the above solutions, in the step S102, the molar ratio of the adipic acid to the N, N-dimethyl-1, 3-propanediamine is (2-2.1): 1; and/or in the step S104, the molar ratio of the N1, N6-bis (3-dimethylaminopropyl) adipamide to the epichlorohydrin is 2: (1.0-1.05); and/or in said step S106, the molar ratio of said N, N-dimethyl-1, 3-propanediamine to said biscationic intermediate is 2: (1.0-1.05); and/or in the step S108, the molar ratio of the epichlorohydrin to the cationic polyamine is 2: (1.0-1.05).
In any of the above technical solutions, in the step S102, the temperature of the reaction condition of the temperature-rising condensation is kept at a temperature of 170 to 180 ℃ for 1 to 3 hours; and/or in the step S104, the reaction condition of the temperature-raising reaction is that the temperature is kept for 2 to 4 hours at the temperature of 50 to 60 ℃; and/or in said step S106, the reaction time of said addition ring-opening reaction is 2 hours to 4 hours; and/or in the step S108, the reaction condition of the temperature-raising reaction is that the temperature is kept for 2 to 4 hours under the temperature condition of 50 to 60 ℃.
In any of the above technical solutions, after the step S100, the method for preparing the cationic emulsifying dispersant for rosin size further includes the following steps: s200, carrying out emulsification complexing surface modification treatment on the rosin size obtained in the step S100 by using a cationic emulsification dispersant.
In any of the above technical solutions, the step S200 specifically includes:
s210, carrying out ultrasonic emulsification on the cationic emulsifying dispersant for the rosin size, the inorganic solvent and the organic solvent which are obtained in the step S100 together to obtain the cationic emulsifying dispersant for the rosin size, and carrying out ultrasonic emulsification surface modification treatment on the cationic emulsifying dispersant;
s220, adopting a complexing agent to carry out coating treatment on the cationic emulsifying and dispersing agent for the rosin size obtained in the step S210, and obtaining the cationic emulsifying and dispersing agent for the rosin size subjected to complexing modification treatment.
In any of the above technical solutions, the step S200 specifically includes the following steps:
step S212, according to the cationic emulsifying dispersant for rosin size: water ═ 70-80: (20-30) mixing the cationic emulsifying dispersant for rosin size obtained by the step S100 with water to obtain a first mixture;
step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate ═ (20-40): (20-40): (20-60) mixing the polylactic acid-glycolic acid copolymer, the acetone, and the ethyl acetate in a mass ratio to obtain a second mixture;
step S216, according to mannitol: alanine: first mixture ═ (1-2): (1-2): (96-98) adding the mannitol and the alanine to the first mixture obtained in the step S212, and uniformly mixing to obtain a third mixture;
step S218, according to the second mixture: third mixture ═ (5-10): (90-95) mixing the second mixture obtained in the step S214 and the third mixture obtained in the step S216, and carrying out ultrasonic emulsification for 1-2 hours to obtain the cationic emulsifying dispersant for rosin size subjected to ultrasonic emulsification surface modification treatment.
In any of the above technical solutions, after the step S218 is performed, the method for preparing the cationic emulsifying dispersant for rosin size further includes the following steps:
step S222, according to the cationic emulsifying dispersant for rosin size: sodium alginate aqueous solution ═ (40-60): (40-60) uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step S218 with the sodium alginate aqueous solution, and performing ultrasonic emulsification for 1-2 hours to obtain a fourth mixture;
s224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotationally vibrated calcium chloride aqueous solution for reaction, and performing centrifugal separation after the reaction to obtain a cationic emulsifying and dispersing agent for rosin size subjected to first complexing modification;
step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid ═ (80-90): (5-10): (5-10) mixing the cationic emulsifying dispersant for rosin size obtained in the step S224 with the chitosan and the acetic acid uniformly, aging for 2-4 hours, performing centrifugal separation, adding water to adjust solid content, and obtaining the cationic emulsifying dispersant for rosin size subjected to second complexing modification.
In order to achieve the second object of the present invention, the embodiment of the present invention provides a cationic emulsifying dispersant for rosin size, which is obtained by the preparation method of the cationic emulsifying dispersant for rosin size according to any one of the embodiments of the present invention.
The cationic emulsifying dispersant for rosin size has low cost, stable property and excellent dispersing performance, can be widely applied to the preparation of cationic dispersed rosin size, and improves the smoothness and uniformity of papermaking chemicals.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
The embodiment of the invention provides a preparation method of a cationic emulsifying dispersant for rosin size, which comprises the following steps: s100, adipic acid, N-dimethyl-1, 3-propane diamine and epoxy chloropropane are used as raw materials, and a cationic emulsifying dispersant for rosin size is obtained through condensation reaction and addition ring-opening reaction.
The raw materials adopted by the embodiment of the invention are low in cost, so that the embodiment of the invention solves the technical problems of high price and high production cost of the polyamide epichlorohydrin emulsification dispersant in the related technology.
In some embodiments of the present invention, the step S100 specifically includes the following steps:
s1, carrying out condensation reaction by adopting a mixture of adipic acid and N, N-dimethyl-1, 3-propane diamine to obtain N1, N6-bis (3-dimethylaminopropyl) adipamide;
Figure BDA0002405257460000061
s2, performing heating reaction on the N1, N6-bis (3-dimethylaminopropyl) adipamide obtained in the step S1 and the epichlorohydrin to obtain a dication intermediate;
Figure BDA0002405257460000071
s3, carrying out addition ring-opening reaction by adopting the mixture of the N, N-dimethyl-1, 3-propane diamine and the dicationic intermediate obtained in the step S2 to obtain cationic polyamine;
Figure BDA0002405257460000072
and S4, performing heating reaction on the epoxy chloropropane and the cationic polyamine obtained in the step S3 to obtain the cationic emulsifying dispersant for the rosin size.
Figure BDA0002405257460000073
The preparation method of the cationic emulsifying dispersant for rosin size provided by the embodiment of the invention is simple and efficient in reaction, and the cationic emulsifying dispersant for rosin size obtained by the embodiment of the invention has the characteristics of high cationic density, stable property and good emulsifying and dispersing effects on rosin.
In some embodiments of the present invention, the step S100 specifically includes the following steps:
step S102, according to adipic acid: n, N-dimethyl-1, 3-propanediamine ═ 1.8 to 2.2: 1, uniformly mixing the adipic acid and the N, N-dimethyl-1, 3-propane diamine in water, heating for dehydration, heating for condensation, cooling and adding water for dilution to obtain N1, N6-bis (3-dimethylaminopropyl) adipamide;
step S104, adding N1, N6-bis (3-dimethylaminopropyl) adipamide: epichlorohydrin 2: (0.8-1.2), uniformly mixing the N1, N6-bis (3-dimethylaminopropyl) adipamide obtained in the step S102 and the epichlorohydrin, heating for reaction, cooling, and obtaining a dicationic intermediate;
step S106, according to the weight ratio of N, N-dimethyl-1, 3-propane diamine: dicationic intermediate ═ 2: (0.8-1.2) a molar ratio of the N, N-dimethyl-1, 3-propanediamine and the dicationic intermediate obtained by the step S104 to be uniformly mixed and subjected to an addition ring-opening reaction to obtain a cationic polyamine;
step S108, according to the epoxy chloropropane: cationic polyamine ═ 2: (0.8-1.2), uniformly mixing the epichlorohydrin with the cationic polyamine obtained in the step S106, heating to react, cooling, adding water to adjust the solid content, and obtaining the cationic emulsifying dispersant for rosin size.
In some embodiments of the present invention, in step S102, the molar ratio of adipic acid to N, N-dimethyl-1, 3-propanediamine is (2-2.1): 1; and/or in the step S104, the molar ratio of the N1, N6-bis (3-dimethylaminopropyl) adipamide to the epichlorohydrin is 2: (1.0-1.05); and/or in said step S106, the molar ratio of said N, N-dimethyl-1, 3-propanediamine to said biscationic intermediate is 2: (1.0-1.05); and/or in the step S108, the molar ratio of the epichlorohydrin to the cationic polyamine is 2: (1.0-1.05).
In some embodiments of the present invention, in step S102, the reaction condition of the temperature-rising condensation is a temperature condition of 170 to 180 degrees celsius, and the temperature is kept for 1 to 3 hours; and/or in the step S104, the reaction condition of the temperature-raising reaction is that the temperature is kept for 2 to 4 hours at the temperature of 50 to 60 ℃; and/or in said step S106, the reaction time of said addition ring-opening reaction is 2 hours to 4 hours; and/or in the step S108, the reaction condition of the temperature-raising reaction is that the temperature is kept for 2 to 4 hours under the temperature condition of 50 to 60 ℃.
In some embodiments of the present invention, after the step S100, the method for preparing the cationic emulsifying dispersant for rosin size further comprises the steps of: s200, carrying out emulsification complexing surface modification treatment on the rosin size obtained in the step S100 by using a cationic emulsification dispersant.
In the above embodiment of the present invention, through the emulsification complexing surface modification treatment, the dispersing performance of the cationic emulsification dispersant for rosin gum to rosin can be further improved, and the surface energy and the surface activity of the cationic emulsification dispersant for rosin gum can be effectively improved. The cationic emulsifying dispersant for rosin size obtained by the embodiment of the invention is used for dispersing rosin, so that the electropositivity of the surface of the rosin can be improved, the rosin size can form stronger electrostatic attraction with negative charges on paper pulp fibers after being precipitated on the surface of the paper pulp fibers, and the smoothness and uniformity of paper can be improved.
In some embodiments of the present invention, the step S200 specifically includes:
s210, carrying out ultrasonic emulsification on the cationic emulsifying dispersant for the rosin size, the inorganic solvent and the organic solvent which are obtained in the step S100 together to obtain the cationic emulsifying dispersant for the rosin size, and carrying out ultrasonic emulsification surface modification treatment on the cationic emulsifying dispersant;
s220, adopting a complexing agent to carry out coating treatment on the cationic emulsifying and dispersing agent for the rosin size obtained in the step S210, and obtaining the cationic emulsifying and dispersing agent for the rosin size subjected to complexing modification treatment.
In some embodiments of the present invention, the step S200 specifically includes the following steps:
step S212, according to the cationic emulsifying dispersant for rosin size: water ═ 70-80: (20-30) mixing the cationic emulsifying dispersant for rosin size obtained by the step S100 with water to obtain a first mixture;
step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate ═ (20-40): (20-40): (20-60) mixing the polylactic acid-glycolic acid copolymer, the acetone, and the ethyl acetate in a mass ratio to obtain a second mixture;
step S216, according to mannitol: alanine: first mixture ═ (1-2): (1-2): (96-98) adding the mannitol and the alanine to the first mixture obtained in the step S212, and uniformly mixing to obtain a third mixture;
step S218, according to the second mixture: third mixture ═ (5-10): (90-95) mixing the second mixture obtained in the step S214 and the third mixture obtained in the step S216, and carrying out ultrasonic emulsification for 1-2 hours to obtain the cationic emulsifying dispersant for rosin size subjected to ultrasonic emulsification surface modification treatment.
In the above embodiment of the present invention, the dispersing property and the surface energy of the cationic emulsifying dispersant for rosin size can be further improved by dissolving the cationic emulsifying dispersant for rosin size in water, adding the organic additive including mannitol and alanine, and finally mixing the inorganic aqueous solution including the cationic emulsifying dispersant for rosin size with the organic solvent including the oil phase of polylactic acid-glycolic acid copolymer and emulsifying the obtained emulsion by ultrasonic.
Specifically, the above embodiment of the present invention aims to mix and ultrasonically emulsify the cationic emulsifying dispersant for rosin size with an organic solvent and an inorganic solvent together to improve the surface activity of the cationic emulsifying dispersant for rosin size, wherein mannitol and alanine are used as a stabilizer and an acid-base regulator in the above embodiment of the present invention, so that the cationic emulsifying dispersant for rosin size is uniformly emulsified in the organic solvent of the oil phase including the polylactic acid-glycolic acid copolymer, and the polylactic acid-glycolic acid copolymer is polymerized from two monomers, namely lactic acid and glycolic acid, and is degradable and has good safety performance and environmental protection performance.
In some embodiments of the present invention, after the step S218 is performed, the method for preparing the cationic emulsifying dispersant for rosin size further comprises the following steps:
step S222, according to the cationic emulsifying dispersant for rosin size: sodium alginate aqueous solution ═ (40-60): (40-60) uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step S218 with the sodium alginate aqueous solution, and performing ultrasonic emulsification for 1-2 hours to obtain a fourth mixture;
s224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotationally vibrated calcium chloride aqueous solution for reaction, and performing centrifugal separation after the reaction to obtain a cationic emulsifying and dispersing agent for rosin size subjected to first complexing modification;
step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid ═ (80-90): (5-10): (5-10) mixing the cationic emulsifying dispersant for rosin size obtained in the step S224 with the chitosan and the acetic acid uniformly, aging for 2-4 hours, performing centrifugal separation, adding water to adjust solid content, and obtaining the cationic emulsifying dispersant for rosin size subjected to second complexing modification.
Sodium alginate is a natural polysaccharide carbohydrate extracted from brown algae such as herba Zosterae Marinae or Sargassum, and has good degradability and stability. The chitosan belongs to reproducible natural high molecular polymers, has the advantages of being natural, non-toxic, degradable and the like, and also has better antibacterial and bacteriostatic properties. In the above embodiment of the invention, the sodium alginate aqueous solution containing the cationic emulsifying dispersant for rosin size is dropped into the rotary oscillation calcium chloride aqueous solution by uniform jet under the action of the high-voltage electrostatic field, so that the sodium alginate reacts with the calcium chloride, and a loose complex coating layer is formed on the surface of the cationic emulsifying dispersant for rosin size, furthermore, in the above embodiment, the chitosan is used for secondary complexing on the surface of the cationic emulsifying dispersant for rosin size, the sodium alginate and the chitosan are used as substances with opposite charges on the surface, and the sodium alginate and the chitosan can form a polyelectrolyte compound through electrostatic acting force, so that the complex treatment can be carried out on the cationic emulsifying dispersant for rosin size by adopting the mutual matching of the sodium alginate and the chitosan, so that a loose distributed complex alternate coating layer is formed on the surface of the cationic emulsifying dispersant for rosin size, thereby further improving the surface energy of the cationic emulsifying dispersant for rosin size.
The above embodiment of the present invention firstly allows the cationic emulsifying dispersant for rosin size to be uniformly emulsified in the organic solvent of the oil phase comprising polylactic acid-glycolic acid copolymer, further performs the first complexation on the surface of the cationic emulsifying dispersant for rosin size subjected to polymer emulsification through the action of the high-voltage electrostatic field by the reaction of sodium alginate and calcium chloride, and finally performs the second complexation on the cationic emulsifying dispersant for rosin size subjected to the first complexation of sodium alginate and calcium chloride through chitosan. Therefore, the cationic emulsifying dispersant for rosin size obtained by the above embodiment of the invention not only has higher surface energy, but also can form electrostatic adsorption between the rosin size and papermaking fibers, thereby improving the quality of the rosin size and the uniformity and smoothness of paper.
Example 1
The embodiment provides a preparation method of a cationic emulsifying dispersant for rosin size, which comprises the following steps.
S102, adding 146 kg (1 mol) of adipic acid, 204 kg (2 mol) of N, N-dimethyl-1, 3-propane diamine and 50 kg of water into a reaction kettle at room temperature, stirring and pre-reacting for 0.5 hour at room temperature, heating to raise the temperature, evaporating the added water generated in the polycondensation reaction, raising the temperature to 170-180 ℃, preserving the temperature for 2 hours, cooling to room temperature, adding 1000 kg of water to obtain N1,N6-bis (3-dimethylaminopropyl) adipamide solution.
Step S104, adding 185 kg (2 mol) of epichlorohydrin to the N obtained in the step S102 in a dropwise manner at room temperature1,N6Stirring and reacting in a solution of-bis (3-dimethylaminopropyl) adipamide for 2 hours, then heating to 50-60 ℃, keeping the temperature for reacting for 3 hours, cooling to room temperature, and obtaining the dication intermediate solution.
And S106, dropwise adding 204 kg (2 mol) of N, N-dimethyl-1, 3-propane diamine into the dication intermediate solution obtained in the step S104 at room temperature, and stirring for reaction for 3 hours to obtain a cationic polyamine solution.
And S108, under the condition of room temperature, adding 185 kg (2 mol) of epoxy chloropropane dropwise into the cationic polyamine solution obtained in the step S106, stirring and reacting for 2 hours, then heating to 50-60 ℃, preserving heat and reacting for 3 hours, cooling to room temperature, adding 5200 kg of water, and adjusting the solid content of the product to 12.5 +/-0.5% to obtain the cationic emulsifying and dispersing agent for rosin size.
Example 2
The embodiment provides a preparation method of a cationic emulsifying dispersant for rosin size, which comprises the following steps.
S102, adding 161 kg (1.1 mol) of adipic acid, 225 kg (2.2 mol) of N, N-dimethyl-1, 3-propane diamine and 50 kg of water into a reaction kettle at room temperature, stirring at room temperature for pre-reaction for 0.5 hour, heating to raise the temperature, evaporating the added water generated in the polycondensation reaction, keeping the temperature for reaction for 2 hours when the temperature is raised to 170-180 ℃, cooling to room temperature, adding 1000 kg of water to obtain N1,N6-bis (3-dimethylaminopropyl) adipamide solution.
Step S104, adding 185 kg (2 mol) of epichlorohydrin to the N obtained in the step S102 in a dropwise manner at room temperature1,N6Stirring and reacting in a solution of-bis (3-dimethylaminopropyl) adipamide for 2 hours, then heating to 50-60 ℃, keeping the temperature for reacting for 3 hours, cooling to room temperature, and obtaining the dication intermediate solution.
And S106, dropwise adding 204 kg (2 mol) of N, N-dimethyl-1, 3-propane diamine into the dication intermediate solution obtained in the step S104 at room temperature, and stirring for reaction for 3 hours to obtain a cationic polyamine solution.
And S108, under the condition of room temperature, adding 185 kg (2 mol) of epoxy chloropropane dropwise into the cationic polyamine solution obtained in the step S106, stirring and reacting for 2 hours, then heating to 50-60 ℃, keeping the temperature and reacting for 3 hours, cooling to room temperature, adding 5500 kg of water, and adjusting the solid content of the product to 12.5 +/-0.5% to obtain the cationic emulsifying and dispersing agent for rosin size.
Example 3
The embodiment provides a preparation method of a cationic emulsifying dispersant for rosin size, which comprises the following steps.
S102, adding 161 kg (1.1 mol) of adipic acid, 235 kg (2.3 mol) of N, N-dimethyl-1, 3-propane diamine and 50 kg of water into a reaction kettle at room temperature, stirring at room temperature for pre-reaction for 0.5 hour, heating to raise the temperature, evaporating the added water generated in the polycondensation reaction, keeping the temperature for reaction for 2 hours when the temperature is raised to 170-180 ℃, cooling to room temperature, adding 1100 kg of water to obtain N1,N6-bis (3-dimethylaminopropyl) adipamide solution.
Step S104, adding 185 kg (2 mol) of epichlorohydrin to the N obtained in the step S102 in a dropwise manner at room temperature1,N6Stirring and reacting in a solution of-bis (3-dimethylaminopropyl) adipamide for 2 hours, then heating to 50-60 ℃, keeping the temperature for reacting for 3 hours, cooling to room temperature, and obtaining the dication intermediate solution.
And S106, dropwise adding 204 kg (2 mol) of N, N-dimethyl-1, 3-propane diamine into the dication intermediate solution obtained in the step S104 at room temperature, and stirring for reaction for 3 hours to obtain a cationic polyamine solution.
And S108, under the condition of room temperature, adding 185 kg (2 mol) of epoxy chloropropane dropwise into the cationic polyamine solution obtained in the step S106, stirring and reacting for 2 hours, then heating to 50-60 ℃, keeping the temperature and reacting for 3 hours, cooling to room temperature, adding 5500 kg of water, and adjusting the solid content of the product to 12.5 +/-0.5% to obtain the cationic emulsifying and dispersing agent for rosin size.
Example 4
This example provides a method for preparing a cationic emulsifying dispersant for rosin size, which is a post-treatment in the following step on the cationic emulsifying dispersant for rosin size prepared in example 1.
Step S212, according to the cationic emulsifying dispersant for rosin size: 70 parts of water: 30, the cationic emulsifying dispersant for rosin gum obtained by example 1 was mixed with water to obtain a first mixture.
Step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate ═ 20: 20: 60 by mass, mixing the polylactic acid-glycolic acid copolymer, the acetone and the ethyl acetate to obtain a second mixture.
Step S216, according to mannitol: alanine: first mixture ═ 1: 1: 98, adding the mannitol and the alanine to the first mixture obtained in the step S212, and mixing them uniformly to obtain a third mixture.
Step S218, according to the second mixture: third mixture 5: 95, mixing the second mixture obtained in the step S214 with the third mixture obtained in the step S216, and carrying out ultrasonic emulsification for 1 hour to obtain the cationic emulsifying dispersant for rosin size subjected to ultrasonic emulsification surface modification treatment. The ultrasonic emulsification was carried out using an ultrasonic emulsifier (power 200W, ultrasonic 1s, interval 1 s).
Step S222, according to the cationic emulsifying dispersant for rosin size: and (3) uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step (S218) with the aqueous sodium alginate solution at a mass ratio of 40:60, and performing ultrasonic emulsification for 1 hour to obtain a fourth mixture. Wherein the concentration of the sodium alginate aqueous solution is 6 wt%.
And S224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotating and oscillating calcium chloride aqueous solution for reaction, and after the reaction, performing centrifugal separation to obtain the cationic emulsifying and dispersing agent for the rosin size, which is subjected to the first complexing modification treatment. Wherein the concentration of the calcium chloride aqueous solution is 4 wt%. The high-voltage electrostatic field is 15kV and is made of an electrostatic field generator. Uniform jet flow is achieved by rotating the injector.
Step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid 80: 10: 10, the cationic emulsifying dispersant for rosin size obtained in the step S224, the chitosan and the acetic acid are uniformly mixed, the mixture is aged for 2 hours and then subjected to centrifugal separation, and water is added to adjust the solid content to 12.5 +/-0.5%, so that the cationic emulsifying dispersant for rosin size subjected to the second complexing modification treatment is obtained.
Example 5
This example provides a method for preparing a cationic emulsifying dispersant for rosin size, which is a post-treatment in the following step on the cationic emulsifying dispersant for rosin size prepared in example 1.
Step S212, according to the cationic emulsifying dispersant for rosin size: 80 parts of water: 20, the cationic emulsifying dispersant for rosin gum obtained by example 1 was mixed with water to obtain a first mixture.
Step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate 40: 40: 20, and mixing the polylactic acid-glycolic acid copolymer, the acetone and the ethyl acetate to obtain a second mixture.
Step S216, according to mannitol: alanine: first mixture ═ 2: 2: 96, the mannitol and the alanine are added to the first mixture obtained in the step S212, and the mixture is mixed uniformly to obtain a third mixture.
Step S218, according to the second mixture: third mixture 10: 90, the second mixture obtained in the step S214 and the third mixture obtained in the step S216 are mixed and subjected to ultrasonic emulsification for 1 hour, and then the cationic emulsifying dispersant for rosin size subjected to the ultrasonic emulsification surface modification treatment is obtained. The ultrasonic emulsification was carried out using an ultrasonic emulsifier (power 200W, ultrasonic 1s, interval 1 s).
Step S222, according to the cationic emulsifying dispersant for rosin size: and (3) uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step (S218) with the aqueous sodium alginate solution at a mass ratio of 60:40, and performing ultrasonic emulsification for 1 hour to obtain a fourth mixture. Wherein the concentration of the sodium alginate aqueous solution is 6 wt%.
And S224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotating and oscillating calcium chloride aqueous solution for reaction, and after the reaction, performing centrifugal separation to obtain the cationic emulsifying and dispersing agent for the rosin size, which is subjected to the first complexing modification treatment. Wherein the concentration of the calcium chloride aqueous solution is 4 wt%. The high-voltage electrostatic field is 15kV and is made of an electrostatic field generator. Uniform jet flow is achieved by rotating the injector.
Step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid 90: 5:5, uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step S224 with the chitosan and the acetic acid, aging for 4 hours, performing centrifugal separation, adding water to adjust the solid content to 12.5 +/-0.5%, and obtaining the cationic emulsifying dispersant for rosin size subjected to second complexing modification.
Example 6
This example provides a method for preparing a cationic emulsifying dispersant for rosin size, which is a post-treatment in the following step on the cationic emulsifying dispersant for rosin size prepared in example 1.
Step S212, according to the cationic emulsifying dispersant for rosin size: 75 parts of water: 25, the cationic emulsifying dispersant for rosin gum obtained by example 1 was mixed with water to obtain a first mixture.
Step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate 30: 30: 40, mixing the polylactic acid-glycolic acid copolymer, the acetone and the ethyl acetate to obtain a second mixture.
Step S216, according to mannitol: alanine: first mixture ═ 1: 2: 97, adding the mannitol and the alanine to the first mixture obtained in the step S212, and mixing them uniformly to obtain a third mixture.
Step S218, according to the second mixture: third mixture 10: 90, the second mixture obtained in the step S214 and the third mixture obtained in the step S216 are mixed and subjected to ultrasonic emulsification for 1 hour, and then the cationic emulsifying dispersant for rosin size subjected to the ultrasonic emulsification surface modification treatment is obtained. The ultrasonic emulsification was carried out using an ultrasonic emulsifier (power 200W, ultrasonic 1s, interval 1 s).
Step S222, according to the cationic emulsifying dispersant for rosin size: and (3) uniformly mixing the rosin size cationic emulsifying dispersant obtained in the step (S218) with the sodium alginate aqueous solution in a mass ratio of 50:50, and performing ultrasonic emulsification for 1 hour to obtain a fourth mixture. Wherein the concentration of the sodium alginate aqueous solution is 6 wt%.
And S224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotating and oscillating calcium chloride aqueous solution for reaction, and after the reaction, performing centrifugal separation to obtain the cationic emulsifying and dispersing agent for the rosin size, which is subjected to the first complexing modification treatment. Wherein the concentration of the calcium chloride aqueous solution is 4 wt%. The high-voltage electrostatic field is 15kV and is made of an electrostatic field generator. Uniform jet flow is achieved by rotating the injector.
Step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid 85: 5: 10, the cationic emulsifying dispersant for rosin size obtained in the step S224, the chitosan and the acetic acid are uniformly mixed, the mixture is aged for 3 hours and then subjected to centrifugal separation, and water is added to adjust the solid content to 12.5 +/-0.5%, so that the cationic emulsifying dispersant for rosin size subjected to the second complexing modification treatment is obtained.
Example 7
This example provides a method for preparing a cationic emulsifying dispersant for rosin size, which is a post-treatment in the following step on the cationic emulsifying dispersant for rosin size prepared in example 1.
Step S212, according to the cationic emulsifying dispersant for rosin size: 70 parts of water: 30, the cationic emulsifying dispersant for rosin gum obtained by example 1 was mixed with water to obtain a first mixture.
Step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate ═ 20: 20: 60 by mass, mixing the polylactic acid-glycolic acid copolymer, the acetone and the ethyl acetate to obtain a second mixture.
Step S216, according to mannitol: alanine: first mixture ═ 2: 2: 96, the mannitol and the alanine are added to the first mixture obtained in the step S212, and the mixture is mixed uniformly to obtain a third mixture.
Step S218, according to the second mixture: third mixture 10: 90, the second mixture obtained in the step S214 and the third mixture obtained in the step S216 are mixed and subjected to ultrasonic emulsification for 1 hour, and then the cationic emulsifying dispersant for rosin size subjected to the ultrasonic emulsification surface modification treatment is obtained. The ultrasonic emulsification was carried out using an ultrasonic emulsifier (power 200W, ultrasonic 1s, interval 1 s).
Step S222, according to the cationic emulsifying dispersant for rosin size: and (3) uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step (S218) with the aqueous sodium alginate solution at a mass ratio of 45:55, and performing ultrasonic emulsification for 1 hour to obtain a fourth mixture. Wherein the concentration of the sodium alginate aqueous solution is 5 wt%.
And S224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotating and oscillating calcium chloride aqueous solution for reaction, and after the reaction, performing centrifugal separation to obtain the cationic emulsifying and dispersing agent for the rosin size, which is subjected to the first complexing modification treatment. Wherein the concentration of the calcium chloride aqueous solution is 3 wt%. The high-voltage electrostatic field is 20kV and is manufactured by an electrostatic field generator. Uniform jet flow is achieved by rotating the injector.
Step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid 80: 10: 10, the cationic emulsifying dispersant for rosin size obtained in the step S224, the chitosan and the acetic acid are uniformly mixed, the mixture is aged for 4 hours and then subjected to centrifugal separation, and water is added to adjust the solid content to 12.5 +/-0.5%, so that the cationic emulsifying dispersant for rosin size subjected to the second complexing modification treatment is obtained.
Performance testing
Respectively adopting the cationic dispersion emulsifier for rosin size obtained in examples 1 to 3 and the PAE dispersion emulsifier purchased in the market, wherein the mass ratio of the emulsifier to the rosin is 1: 1, feeding, preparing a rosin adhesive emulsion by a high-pressure homogenization method, wherein the mass ratio of rosin to liquid aluminum sulfate is 1: 2, adding liquid aluminum sulfate into the homogenized rosin latex, and uniformly stirring to obtain a finished product rosin gum. Particle size and polydispersity were determined by a nanosizer (Zetasizer Nano ZS 90).
Table 1: characterization of the Properties of the cationic Dispersion emulsifiers
Figure BDA0002405257460000181
Figure BDA0002405257460000191
As can be seen from the data in the table above, the rosin size obtained by using the cationic emulsifying dispersant for rosin size of the embodiment of the invention has more uniform particle size distribution, smaller particle size and better emulsion storage stability.
In the present invention, the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more unless expressly limited otherwise. The terms "mounted," "connected," "fixed," and the like are to be construed broadly, and for example, "connected" may be a fixed connection, a removable connection, or an integral connection; "coupled" may be direct or indirect through an intermediary. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the cationic emulsifying dispersant for the rosin size is characterized by comprising the following steps:
s100, adipic acid, N-dimethyl-1, 3-propane diamine and epoxy chloropropane are used as raw materials, and a cationic emulsifying dispersant for rosin size is obtained through condensation reaction and addition ring-opening reaction.
2. The method for preparing the cationic emulsifying dispersant for rosin size according to claim 1, wherein the step S100 specifically comprises the steps of:
s1, carrying out condensation reaction by adopting a mixture of adipic acid and N, N-dimethyl-1, 3-propane diamine to obtain N1, N6-bis (3-dimethylaminopropyl) adipamide;
Figure FDA0002405257450000011
s2, performing heating reaction on the N1, N6-bis (3-dimethylaminopropyl) adipamide obtained in the step S1 and the epichlorohydrin to obtain a dication intermediate;
Figure FDA0002405257450000012
s3, carrying out addition ring-opening reaction by adopting the mixture of the N, N-dimethyl-1, 3-propane diamine and the dicationic intermediate obtained in the step S2 to obtain cationic polyamine;
Figure FDA0002405257450000013
and S4, performing heating reaction on the epoxy chloropropane and the cationic polyamine obtained in the step S3 to obtain the cationic emulsifying dispersant for the rosin size.
Figure FDA0002405257450000021
3. The method for preparing the cationic emulsifying dispersant for rosin size according to claim 1, wherein the step S100 specifically comprises the steps of:
step S102, according to adipic acid: n, N-dimethyl-1, 3-propanediamine ═ 1.8 to 2.2: 1, uniformly mixing the adipic acid and the N, N-dimethyl-1, 3-propane diamine in water, heating for dehydration, heating for condensation, cooling and adding water for dilution to obtain N1, N6-bis (3-dimethylaminopropyl) adipamide;
step S104, adding N1, N6-bis (3-dimethylaminopropyl) adipamide: epichlorohydrin 2: (0.8-1.2), uniformly mixing the N1, N6-bis (3-dimethylaminopropyl) adipamide obtained in the step S102 and the epichlorohydrin, heating for reaction, cooling, and obtaining a dicationic intermediate;
step S106, according to the weight ratio of N, N-dimethyl-1, 3-propane diamine: dicationic intermediate ═ 2: (0.8-1.2) a molar ratio of the N, N-dimethyl-1, 3-propanediamine and the dicationic intermediate obtained by the step S104 to be uniformly mixed and subjected to an addition ring-opening reaction to obtain a cationic polyamine;
step S108, according to the epoxy chloropropane: cationic polyamine ═ 2: (0.8-1.2), uniformly mixing the epichlorohydrin with the cationic polyamine obtained in the step S106, heating to react, cooling, adding water to adjust the solid content, and obtaining the cationic emulsifying dispersant for rosin size.
4. The method for preparing the cationic emulsifying dispersant for rosin size according to claim 3,
in the step S102, the molar ratio of the adipic acid to the N, N-dimethyl-1, 3-propanediamine is (2-2.1): 1; and/or
In the step S104, the molar ratio of N1, N6-bis (3-dimethylaminopropyl) adipamide to epichlorohydrin is 2: (1.0-1.05); and/or
In the step S106, the molar ratio of the N, N-dimethyl-1, 3-propanediamine to the biscationic intermediate is 2: (1.0-1.05); and/or
In the step S108, the molar ratio of the epichlorohydrin to the cationic polyamine is 2: (1.0-1.05).
5. The method for preparing the cationic emulsifying dispersant for rosin size according to claim 3,
in the step S102, the temperature of the reaction condition of the temperature-rising condensation is kept at 170 to 180 ℃ for 1 to 3 hours; and/or
In the step S104, the temperature of the temperature-raising reaction is maintained at 50 to 60 ℃ for 2 to 4 hours; and/or
In the step S106, the reaction time of the addition ring-opening reaction is 2 to 4 hours; and/or
In the step S108, the reaction condition of the temperature-raising reaction is a temperature condition of 50 to 60 degrees celsius, and the temperature is maintained for 2 to 4 hours.
6. The method for preparing cationic emulsifying dispersant for rosin size according to any one of claims 1 to 5, characterized in that after said step S100, it further comprises the steps of:
s200, carrying out emulsification complexing surface modification treatment on the rosin size obtained in the step S100 by using a cationic emulsification dispersant.
7. The method for preparing the cationic emulsifying dispersant for rosin size according to claim 6, wherein the step S200 specifically comprises:
s210, carrying out ultrasonic emulsification on the cationic emulsifying dispersant for the rosin size, the inorganic solvent and the organic solvent which are obtained in the step S100 together to obtain the cationic emulsifying dispersant for the rosin size, and carrying out ultrasonic emulsification surface modification treatment on the cationic emulsifying dispersant;
s220, adopting a complexing agent to carry out coating treatment on the cationic emulsifying and dispersing agent for the rosin size obtained in the step S210, and obtaining the cationic emulsifying and dispersing agent for the rosin size subjected to complexing modification treatment.
8. The method for preparing the cationic emulsifying dispersant for rosin size according to claim 6, wherein the step S200 specifically comprises the steps of:
step S212, according to the cationic emulsifying dispersant for rosin size: water ═ 70-80: (20-30) mixing the cationic emulsifying dispersant for rosin size obtained by the step S100 with water to obtain a first mixture;
step S214, according to the polylactic acid-glycolic acid copolymer: acetone: ethyl acetate ═ (20-40): (20-40): (20-60) mixing the polylactic acid-glycolic acid copolymer, the acetone, and the ethyl acetate in a mass ratio to obtain a second mixture;
step S216, according to mannitol: alanine: first mixture ═ (1-2): (1-2): (96-98) adding the mannitol and the alanine to the first mixture obtained in the step S212, and uniformly mixing to obtain a third mixture;
step S218, according to the second mixture: third mixture ═ (5-10): (90-95) mixing the second mixture obtained in the step S214 and the third mixture obtained in the step S216, and carrying out ultrasonic emulsification for 1-2 hours to obtain the cationic emulsifying dispersant for rosin size subjected to ultrasonic emulsification surface modification treatment.
9. The method of claim 8, wherein after the step S218, the method further comprises the steps of:
step S222, according to the cationic emulsifying dispersant for rosin size: sodium alginate aqueous solution ═ (40-60): (40-60) uniformly mixing the cationic emulsifying dispersant for rosin size obtained in the step S218 with the sodium alginate aqueous solution, and performing ultrasonic emulsification for 1-2 hours to obtain a fourth mixture;
s224, under the action of a high-voltage electrostatic field, uniformly jetting the fourth mixture obtained in the step S222 into a rotationally vibrated calcium chloride aqueous solution for reaction, and performing centrifugal separation after the reaction to obtain a cationic emulsifying and dispersing agent for rosin size subjected to first complexing modification;
step S226, according to the cationic emulsifying dispersant for rosin size: and (3) chitosan: acetic acid ═ (80-90): (5-10): (5-10) mixing the cationic emulsifying dispersant for rosin size obtained in the step S224 with the chitosan and the acetic acid uniformly, aging for 2-4 hours, performing centrifugal separation, adding water to adjust solid content, and obtaining the cationic emulsifying dispersant for rosin size subjected to second complexing modification.
10. A cationic emulsifying dispersant for rosin size is characterized in that,
the cationic emulsifying dispersant for rosin size is obtained by the method for preparing the cationic emulsifying dispersant for rosin size according to any one of claims 1 to 9.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5117058A (en) * 1990-11-09 1992-05-26 Baker Hughes Incorporated Cationic amide/ester compositions as demulsifiers
CN102906209A (en) * 2010-05-20 2013-01-30 佐治亚-太平洋化工品有限公司 hermosetting creping adhesive with reactive modifiers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5117058A (en) * 1990-11-09 1992-05-26 Baker Hughes Incorporated Cationic amide/ester compositions as demulsifiers
CN102906209A (en) * 2010-05-20 2013-01-30 佐治亚-太平洋化工品有限公司 hermosetting creping adhesive with reactive modifiers

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