CN112796157A - AKD/ASA composite papermaking sizing agent and preparation method and application thereof - Google Patents

AKD/ASA composite papermaking sizing agent and preparation method and application thereof Download PDF

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CN112796157A
CN112796157A CN202110034063.9A CN202110034063A CN112796157A CN 112796157 A CN112796157 A CN 112796157A CN 202110034063 A CN202110034063 A CN 202110034063A CN 112796157 A CN112796157 A CN 112796157A
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akd
asa
emulsion
oil
mixing
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CN112796157B (en
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于得海
王之勒
赵锐
胡飞鸿
姬丹丹
张海光
王哲
刘温霞
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Shandong Jiqing Technology Service Co ltd
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Qilu University of Technology
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H17/17—Ketenes, e.g. ketene dimers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, 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
    • D21H19/38—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

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

The invention provides a preparation method of AKD/ASA composite emulsion, which comprises the following steps: mixing AKD oil with perfluorohexane, and uniformly stirring to obtain AKD-P oil; mixing montmorillonite water dispersion with acetone, ammonium monohydrate and hexadecyl trimethyl siloxane, and uniformly dispersing to obtain a mixed solution I; adding tridecafluorooctyltriethoxysilane into the mixed solution I, and performing ultrasonic dispersion to obtain a mixed solution II; drying the mixed solution II to obtain modified MMT powder; mixing the modified MMT powder and ASA, dispersing uniformly, adding AKD-P oil, mixing, and performing ultrasonic emulsification to obtain AKD-P/ASA emulsion; and mixing the AKD-P/ASA emulsion with a sodium dodecyl sulfate aqueous solution, and performing ultrasonic emulsification to obtain the ASA/AKD composite emulsion. The emulsion is wrapped by the AKD in the outer oil phase, so that the contact between the ASA and the water phase is avoided, the purpose of avoiding ASA hydrolysis is achieved, and the emulsion has the double sizing performances of the AKD and the ASA, and can further improve the water resistance of sizing paper.

Description

AKD/ASA composite papermaking sizing agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of papermaking, in particular to an alkyl ketene dimer/alkenyl succinic anhydride composite papermaking sizing agent emulsion and a preparation method and application thereof.
Background
The twenty-century paper making industry changes from an acid paper making system to medium-alkaline paper making, is an innovative change of a paper making process, greatly improves the paper quality, expands the filler range, reduces the pulp consumption and the energy consumption, lightens the environmental pollution and prolongs the service life of equipment. According to data statistics, the cultural paper produced by the medium and alkaline sizing accounts for 60-65% of the total amount of the cultural paper in the beginning of the 80 th year in Europe, the cultural paper reaches 95% in the 90 th year, and the medium and alkaline sizing proportion of the high-grade paper in the United states at the same time is increased from 15% to more than 90%. Since 1989, the use of medium-and alkaline sizing in production has begun, and the application thereof has gradually become popular in recent years, and Alkyl Ketene Dimer (AKD) and Alkenyl Succinic Anhydride (ASA) are mainly used at present.
AKD is unsaturated lactone, is water-insoluble waxy solid at normal temperature, can be used as a papermaking sizing agent, but must be prepared into emulsion before use, and is one of the sizing agents commonly used for alkaline sizing in the paper industry at present. The other commonly used papermaking sizing agent, namely alkenyl succinic anhydride, is liquid at normal temperature, anhydride in a molecular structure of the alkenyl succinic anhydride is very easy to hydrolyze, the storage stability is poor, the alkenyl succinic anhydride needs to be emulsified in a workshop on site, and a hydrolysis product of the alkenyl succinic anhydride is easy to deposit on a paper machine to cause papermaking obstacle, so that the application of the alkenyl succinic anhydride is limited to a certain extent. The lactone ring in the AKD emulsion has low hydrolysis speed, emulsion drops are solid particles at normal temperature, the emulsion has good storage property, the emulsion prepared by the good emulsification process can be placed for 2-3 months, the sizing efficiency is high, the cost is relatively low, and the advantages promote the wide application of the AKD emulsion. However, compared with alkenyl succinic anhydride, AKD emulsion has storage requirement, and the emulsion is required to have long-term emulsion droplet aggregation resistance and other properties, and the emulsification process requirement is more severe. The AKD emulsifying process is generally heating to melt, then adding dispersant, surfactant, gelatinized cationic starch and the like, homogenizing and emulsifying after premixing, cooling and canning after homogenizing. The surfactant added in the emulsification process can reduce the sizing efficiency, easily generate air bubbles, bring the foaming problem to a paper making system and even generate paper defects. Therefore, the development of an efficient AKD emulsifying system and the reduction of the dosage of the surfactant even without the surfactant are beneficial to improving the AKD sizing efficiency, and the AKD sizing agent is suitable for the production requirements of paper-making enterprises and the requirements of the current green production. Patent application CN104499361A provides a preparation method of AKD sizing agent of nano microcrystalline cellulose, which avoids the use of surface sizing agent, can be used for both surface sizing and internal sizing of paper pulp, and significantly improves the sizing degree of paper industry, but the current preparation method of microcrystalline cellulose is complex and expensive, and is not beneficial to wide industrial application. Patent application CN103774496A discloses an AKD emulsion stabilized by glutamic acid, hydrotalcite and polydiallyldimethylammonium chloride together, and the patent publication mentions that the AKD emulsion stabilized by glutamic acid and hydrotalcite alone is unstable, the emulsion formed by adding polydiallyldimethylammonium chloride has good stability and sizing performance, and a cationic surfactant (polydiallyldimethylammonium chloride) is still used in the emulsion preparation process. Patent application CN101942780A discloses a method for jointly emulsifying AKD by chitosan and nano titanium dioxide, which has the advantages of simple emulsification process, high AKD emulsion sizing efficiency and high curing speed, but the emulsion drop coalescence stability is still to be improved. In view of the wide use of AKD and the problems existing at present, a new AKD emulsion preparation technology needs to be further researched to prepare a sizing agent which has high sizing efficiency and is suitable for modern paper-making enterprises.
ASA sizing agents have high reactivity, low sizing cost and fast curing rate, and are widely used for internal sizing of high-grade paper and paperboard, in particular for large high-speed paper machines with internal coating. However, ASA is a neutral sizing agent for papermaking with high reactivity, the hydrolysis speed is high, the sizing effect is reduced after the emulsion is stored for more than 1 hour at room temperature, the hydrolysate can cause paper making obstruction and the sizing efficiency is reduced, so when ASA is used, the ASA is required to be emulsified quickly, and the emulsified emulsion is required to be used as soon as possible. Alkenyl Succinic Anhydride (ASA) is very easy to hydrolyze, alcoholysis and ammonolysis, so alcohol, carboxylic acid and ammonia compounds are not suitable for being used as an emulsifier for ASA. At present, the ASA sizing agent is emulsified in situ mainly by using cationic starch and low molecular surfactant and is used immediately. However, starch needs to be gelatinized and cooled before use, which makes the ASA emulsification process rather complicated, difficult to control, and often causes problems with deposition, felt blockage, etc. The surfactant therein also has a certain adverse effect on sizing and also causes a certain pollution to the environment. At present, the research and the achievement of the emulsification preparation of the ASA sizing agent are gradually enriched. US patent application US6346554 discloses a method for stabilizing ASA emulsions using natural vegetable gums which purportedly increase ASA application efficiency by increasing ASA retention on the fibers, reducing ASA hydrolysis and consequent deposition problems and forming a more uniform film on the fiber surface. US patent application US5962555A discloses a method for emulsifying ASA using a mixture of ionene polymers which not only increase sizing efficiency but also have a bactericidal effect and polyethyleneimine. Although these inventions eliminate the inconvenience of starch gelatinization in handling, they still require the addition of about 2% surfactant to obtain a stable ASA emulsion. Patent application CN1214093A discloses a method for stabilizing ASA emulsions with anionic microparticle retention aids for paper making such as bentonite, colloidal silica, organic microparticles with small amounts of surfactant and chelating agent, which combines microparticle retention aids with sizing agents, simplifies the operation and reduces the amount of surfactant used. However, the adverse effect of the surfactant cannot be completely avoided, and the addition amount of the particulate component is too large, so that the concentration of the prepared ASA emulsion is low, the storage of the emulsion is not facilitated, and the ASA is hydrolyzed seriously. Patent application CN105056830A discloses a biodegradable solid particle emulsifier based on modified nano-cellulose crystal particles and an emulsified ASA sizing agent thereof, wherein the emulsified emulsion has good stability and can meet the general production requirements, but the emulsion has general stability, the sizing activity can only be kept for about 3 hours, and the limitation of ASA used in field emulsification still can not be removed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the oil-in-water/oil (W/O/O) type AKD/ASA composite emulsion which is synergistically emulsified and stabilized by sodium dodecyl sulfate and montmorillonite (MMT), and the emulsion has higher stability and sizing activity as a papermaking sizing agent.
In order to achieve the purpose, the invention adopts the following technical scheme.
A preparation method of AKD/ASA composite emulsion comprises the following steps:
(1) mixing AKD oil with perfluorohexane, and uniformly stirring to obtain AKD-P oil;
(2) mixing Montmorillonite (MMT) water dispersion with acetone, ammonium monohydrate and hexadecyl trimethyl siloxane, and uniformly dispersing to obtain a mixed solution I; adding tridecafluorooctyltriethoxysilane into the mixed solution I, and performing ultrasonic dispersion to obtain a mixed solution II; drying the mixed solution II to obtain modified MMT powder;
(3) mixing the modified MMT powder and ASA, dispersing uniformly, adding AKD-P oil, mixing, and performing ultrasonic emulsification to obtain AKD-P/ASA emulsion;
(4) and mixing the AKD-P/ASA emulsion with a sodium dodecyl sulfate aqueous solution, and performing ultrasonic emulsification to obtain the ASA/AKD composite emulsion.
The AKD oil is AKD which is liquid at normal temperature, and the liquid AKD is branched chain saturated fatty acid type alkyl ketene dimer with a large amount of isomers after part of unsaturated fatty acid is subjected to catalytic hydroisomerization.
The mass ratio of the AKD oil to the perfluorohexane is 1: 0.05-0.5.
The MMT is a flaky nano particle with the diameter of 25-100nm and the thickness of 2-10 nm.
The mass fraction of MMT, acetone and ammonia monohydrate in the mixed solution I is 0.05-2%, 0.1-1% and 0.5-2%.
The dosage of the hexadecyl trimethyl siloxane is 2-30% of the mass of the MMT.
The dosage of the tridecafluorooctyltriethoxysilane accounts for 5-20% of the mass of the MMT.
The mass ratio of the modified MMT powder to the ASA is 1: 20-100.
The mass ratio of the AKD-P oil to the ASA is 1: 0.1-2.
The mass ratio of the AKD-P/ASA emulsion to the sodium dodecyl sulfate aqueous solution is 1: 0.5-10.
The mass percentage content of the sodium dodecyl sulfate aqueous solution is 0.1-2%, preferably 0.2-1%;
the dispersing mode can be mechanical stirring or ultrasonic dispersing; the power of the ultrasonic wave is 500-3000W.
An AKD/ASA composite emulsion obtained by the preparation method.
An application of the ASA/AKD composite emulsion in the preparation of paper.
The ASA/AKD composite emulsion is used as a paper sizing agent.
The invention has the following advantages:
the AKD/ASA composite papermaking sizing agent emulsion comprises MMT nano-particles modified by hexadecyl trimethyl siloxane and tridecafluorooctyl triethoxy silane, ASA oil containing perfluorohexane, liquid AKD oil and a sodium dodecyl sulfate surfactant. Hydroxyl on the surface of the MMT nano-particles is modified by grafting so that the surface of the MMT nano-particles obtains a group- (CF) of a fluorocarbon oil phase2)2(CF2)5CF3And a group- (CH) of a hydrocarbon-philic oil phase2)15CH3While the AKD-P oil has fluorocarbon groups, thereby imparting to the MMT nanoparticles the ability to emulsify simultaneously stabilized AKD-P and ASA and forming an oil-in-oil (O/O) emulsion. And finally, emulsifying the AKD-P/ASA emulsion by using the sodium dodecyl sulfate to form the oil-in-water-in-oil (W/O/O) type AKD/ASA composite emulsion, wherein the outer layer is coated with AKD, so that the ASA oil phase at the innermost layer is prevented from contacting with the water phase at the outermost layer, and the emulsion has high stability and strong hydrolysis resistance. In addition, compared with the traditional waxy AKD papermaking sizing agent, the liquid AKD is used without melting the AKD at high temperature, and the AKD can be emulsified at normal temperature, so that the steam consumption is greatly reduced, and the production cost is reduced. The liquid AKD being partially unsaturatedAfter catalytic hydrogenation isomerization, fatty acid is changed into branched chain saturated fatty acid with a large number of isomers, under the condition that the total carbon number is not changed, the number of straight chain carbon is reduced, the produced paper is less prone to slipping, and the problem that the paper is prone to slipping is effectively solved.
The AKD/ASA composite sizing agent finally prepared by the invention is W/O/O composite emulsion type emulsion, wherein ASA is coated by AKD and is distributed in water in the form of spherical dispersed liquid drops. The modified MMT is adsorbed at an oil-oil interface between AKD and ASA in a form of solid particles to stabilize the AKD-ASA interface to form an oil-oil emulsion, an AKD/ASA emulsion droplet exists as a dispersed phase of the emulsion droplet, a continuous phase is a sodium dodecyl sulfate aqueous solution, and the O/O/W type AKD/ASA emulsion droplet finally obtained avoids the contact between ASA and a water phase due to the wrapping of an outer oil phase AKD, so that the purpose of avoiding ASA hydrolysis is achieved, and the modified MMT has the double sizing performances of AKD and ASA and can further improve the water resistance of sizing paper.
Drawings
FIG. 1 is a micrograph of the AKD/ASA composite emulsion prepared in example 2.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
EXAMPLE 1 preparation of AKD/ASA composite emulsion
(1) Mixing AKD oil and perfluorohexane according to the mass ratio of 1:0.05, and uniformly stirring to obtain AKD-P oil;
(2) dispersing 1 part by weight of MMT (the average width of a single particle is 25nm, the thickness of the single particle is 2 nm) in water to prepare a dispersion liquid with the mass fraction of 0.05 percent, adding 2 parts by weight of acetone, 10 parts by weight of ammonium monohydrate and 0.02 part by weight of hexadecyl trimethyl siloxane, mixing, and carrying out ultrasonic treatment at 25 ℃ for 1 hour at 500W to obtain a mixed solution I; then adding 0.05 part by weight of tridecafluorooctyltriethoxysilane, and continuing to perform ultrasonic treatment for 1 hour to obtain a mixed solution II; drying the mixed solution II at 105 ℃ to obtain modified MMT powder;
(3) mixing 1 weight part of modified MMT powder and 20 weight parts of ASA, performing ultrasonic dispersion for 1 hour at 500W, adding 200 weight parts of AKD-P oil, and performing ultrasonic emulsification for 15 minutes at 500W to obtain oil-in-oil (O/O) type AKD-P/ASA emulsion;
(4) mixing 2 parts by weight of AKD-P/ASA emulsion with 1 part by weight of sodium dodecyl sulfate aqueous solution with the mass concentration of 0.1%, and ultrasonically emulsifying for 15 minutes at 500W to obtain the oil-in-water-in-oil (O/O/W) type ASA/AKD composite emulsion.
Example 2 preparation of AKD/ASA composite emulsion
(1) Mixing AKD oil and perfluorohexane according to the mass ratio of 1:1, and uniformly stirring to obtain AKD-P oil;
(2) dispersing 1 part by weight of MMT (the average width of a single particle is 45nm, the thickness of the single particle is 5 nm) in water to prepare a dispersion liquid with the mass fraction of 1%, adding 10 parts by weight of acetone, 20 parts by weight of ammonium monohydrate and 0.2 part by weight of hexadecyl trimethyl siloxane, mixing, and carrying out ultrasonic treatment at 25 ℃ for 1 hour at 1000W to obtain a mixed solution I; then adding 0.1 part by weight of tridecafluorooctyltriethoxysilane, and continuing to perform ultrasonic treatment for 1 hour to obtain a mixed solution II; drying the mixed solution II at 105 ℃ to obtain modified MMT powder;
(3) mixing 1 weight part of modified MMT powder and 60 weight parts of ASA, performing ultrasonic dispersion for 1 hour at 1000W, adding 60 weight parts of AKD-P oil, and performing ultrasonic emulsification for 15 minutes at 1000W to obtain oil-in-oil (O/O) type AKD-P/ASA emulsion;
(4) mixing 1 part by weight of AKD-P/ASA emulsion with 5 parts by weight of sodium dodecyl sulfate aqueous solution with the mass concentration of 0.5%, and ultrasonically emulsifying for 15 minutes at 1000W to obtain the oil-in-water-in-oil (O/O/W) ASA/AKD composite emulsion. The composite emulsion obtained is observed under a microscope, and the picture is shown in figure 1: the AKD/ASA composite emulsion takes sodium dodecyl sulfate aqueous solution as a continuous phase, and takes the AKD/ASA emulsion as a disperse phase to be uniformly distributed; the AKD/ASA emulsion is adsorbed at the oil-oil interface between AKD and ASA in the form of solid particles by modifying MMT to form an oil-oil emulsion in which ASA is coated with AKD.
EXAMPLE 3 preparation of AKD/ASA composite emulsion
(1) Mixing AKD oil and perfluorohexane according to the mass ratio of 1:2, and uniformly stirring to obtain AKD-P oil;
(2) dispersing 2 parts by weight of MMT (the average width of a single particle is 100nm and the thickness of the single particle is 10 nm) in water to prepare a dispersion liquid with the mass fraction of 2%, adding 1 part by weight of acetone, 2 parts by weight of ammonium monohydrate and 0.6 part by weight of hexadecyl trimethyl siloxane, mixing, and carrying out ultrasonic treatment at the temperature of 25 ℃ for 1 hour at 3000W to obtain a mixed solution I; then adding 0.4 weight part of tridecafluorooctyltriethoxysilane, and continuing to perform ultrasonic treatment for 1 hour to obtain a mixed solution II; drying the mixed solution II at 105 ℃ to obtain modified MMT powder;
(3) mixing 1 weight part of modified MMT powder and 100 weight parts of ASA, carrying out ultrasonic dispersion for 1 hour at 3000W, then adding 10 weight parts of AKD-P oil for mixing, and carrying out ultrasonic emulsification for 15 minutes at 3000W to obtain oil-in-oil (O/O) type AKD-P/ASA emulsion;
(4) mixing 1 part by weight of AKD-P/ASA emulsion with 10 parts by weight of 1% sodium dodecyl sulfate aqueous solution, and carrying out ultrasonic emulsification at 3000W for 15 minutes to obtain the oil-in-water-in-oil (O/O/W) ASA/AKD composite emulsion.
Comparative example 1
A process for preparing a composite ASA size emulsion as described in example 3 of patent 201310108087.X (a process for preparing a solid particle emulsion-stabilized papermaking size) except that paraffin oil was replaced with an AKD oil prepared ASA/AKD composite emulsion size.
Performance measurement of paper sizing agent Using AKD/ASA composite emulsion
(1) Paper making of sized paper
Sizing by an internal sizing method. Before sizing, diluting AKD/ASA composite papermaking sizing agent emulsion to 0.5 percent, adjusting the pulp concentration to 1 percent, adding 1 percent of aluminum sulfate (relative to the mass percent of oven dry pulp) into pulp at the stirring speed of 1000rpm, then adjusting the pH value of the pulp to 7-8.5 by using 1 mol/L of sodium hydroxide solution, then sequentially adding the diluted AKD/ASA composite papermaking sizing agent emulsion (the using amount is 0.5 percent, the percentage of the total mass of ASA/AKD relative to the total mass of oven dry pulp) and 0.03 percent (relative to the mass percent of oven dry pulp) of cationic polyacrylamide, stirring for 2 minutes at the shearing speed of 1000rpm by using a stirrer, standing for 30 seconds, and then using a PTI paper sheet papermaking machine (model: 3AKWT, origin: Olympic paper pulp)Utilizing) making handsheets with a handsheet basis weight of 60 g/m2(T205 om-88, TAPPI), the sheet making system selects a Kaiser method manual sheet making mode to make sheets according to the ISO5289/2 and DIN54358 standards. The handsheets produced were dried at 105 ℃ and then the moisture of the paper was equilibrated at room temperature for 24h with an ambient humidity of 50%.
(2) Sizing degree measuring method
Sizing performance was evaluated by measuring the degree of sizing of paper made (GB/T5405-2002). Before measurement, the paper was cut into square pieces of 30X 30mm and allowed to stand at 25 ℃ under a 50% humidity environment to equilibrate the moisture for 24 hours. The paper is folded at four sides to form a boat-shaped structure with the bottom surface area of about 20 multiplied by 20mm, then the boat-shaped structure floats in ammonium thiocyanate dilute solution with the concentration of 2 percent, 0.5 mu L of ferric chloride solution with the mass concentration of 1 percent is dripped on the upper part of the boat-shaped paper by a rubber head dropper, and the timing is ended by a stopwatch when red spots appear in the middle of the ferric chloride solution, and the timing is the sizing degree of the paper sample. The front and back sides of the test sample were measured 10 times each and the average value was taken.
(3) Method for measuring average particle diameter of liquid drop
The diameters of 100 emulsion droplets observed under a microscope are counted by using particle size counting software carried by an optical microscope, and the average value is taken, namely the average particle size of the droplets.
TABLE 1 Properties of different sizing agents
Figure DEST_PATH_IMAGE001
According to the table 1, the average particle size of the liquid drops of the AKD/ASA composite emulsion prepared by the invention is smaller, and the emulsion is not precipitated by any phase body or demulsified after being placed for 30 days, which shows that the AKD/ASA composite emulsion prepared by the invention has good stability; when the amount of the sizing agent is 0.2 percent (the mass ratio of ASA/AKD to absolutely dry pulp), the paper sheet sizing degree of the internally sized paper is 2400-2600 seconds, which shows that the sizing performance of the emulsion is excellent, and when the sizing agent is used after being stored for 30 days, the sizing degree of the sized paper is 2100-2500 seconds, which shows that the anti-hydrolysis performance of the emulsion is good, the sizing degree is attenuated (about 100-300 seconds) along with the standing time (within 30 days), because the sizing activity generated by the hydrolysis of partial AKD is attenuated, but the ASA of the inner layer is effectively protected, so that the sizing activity of the sizing agent still keeps a high level.

Claims (9)

1. The preparation method of the AKD/ASA composite emulsion is characterized by comprising the following steps:
(1) mixing AKD oil with perfluorohexane, and uniformly stirring to obtain AKD-P oil;
(2) mixing montmorillonite water dispersion with acetone, ammonium monohydrate and hexadecyl trimethyl siloxane, and uniformly dispersing to obtain a mixed solution I; adding tridecafluorooctyltriethoxysilane into the mixed solution I, and performing ultrasonic dispersion to obtain a mixed solution II; drying the mixed solution II to obtain modified MMT powder;
(3) mixing the modified MMT powder and ASA, dispersing uniformly, adding AKD-P oil, mixing, and performing ultrasonic emulsification to obtain AKD-P/ASA emulsion;
(4) and mixing the AKD-P/ASA emulsion with a sodium dodecyl sulfate aqueous solution, and performing ultrasonic emulsification to obtain the ASA/AKD composite emulsion.
2. The method according to claim 1, wherein the AKD oil is AKD that is liquid at room temperature; the mass ratio of the AKD oil to the perfluorohexane is 1: 0.05-0.5.
3. The method of claim 1, wherein the montmorillonite is a nano-particle in the form of a flake having a diameter of 25-100nm and a thickness of 2-10 nm;
the mass fraction of montmorillonite in the mixed solution I is 0.05-2%, the mass fraction of acetone is 0.1-1%, and the mass fraction of ammonium monohydrate is 0.5-2%;
the dosage of the hexadecyl trimethyl siloxane is 2-30% of the mass of the montmorillonite; the dosage of the tridecafluorooctyltriethoxysilane accounts for 5 to 20 percent of the mass of the montmorillonite.
4. The method of claim 1, wherein the modified MMT powder to ASA mass ratio is 1: 20-100; the mass ratio of the AKD-P oil to the ASA is 1: 0.1-2.
5. The preparation method according to claim 1, wherein the mass ratio of the AKD-P/ASA emulsion to the aqueous solution of sodium dodecyl sulfate is 1: 0.5-10; the mass percentage of the sodium dodecyl sulfate aqueous solution is 0.1-2%.
6. The preparation method according to claim 1, wherein the dispersing mode can be mechanical stirring or ultrasonic dispersing; the power of the ultrasonic wave is 500-3000W.
7. An AKD/ASA composite emulsion obtained by the production method as defined in any one of claims 1 to 6.
8. Use of an ASA/AKD composite emulsion as defined in claim 7 for the preparation of paper.
9. Use according to claim 8, characterized in that the ASA/AKD composite emulsion is used as a paper sizing agent.
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JP2003313251A (en) * 2002-04-21 2003-11-06 Seiko Pmc Corp Polymeric dispersant, aqueous dispersion, sizing agent and paper
CN103194934A (en) * 2013-03-29 2013-07-10 华南理工大学 Preparation method of paper making sizing agent formed by emulsification of flaky solid particles
CN103233392A (en) * 2013-03-29 2013-08-07 华南理工大学 Preparation method of solid particle emulsified and stabilized papermaking sizing agent
CN111749046A (en) * 2019-08-29 2020-10-09 齐鲁工业大学 Alkyl ketene dimer sizing agent and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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CN1219988A (en) * 1996-03-29 1999-06-16 斯托拉·科帕伯格斯·伯格斯拉格斯公司 Size composition, method for its preparation and use thereof
JP2003313251A (en) * 2002-04-21 2003-11-06 Seiko Pmc Corp Polymeric dispersant, aqueous dispersion, sizing agent and paper
CN103194934A (en) * 2013-03-29 2013-07-10 华南理工大学 Preparation method of paper making sizing agent formed by emulsification of flaky solid particles
CN103233392A (en) * 2013-03-29 2013-08-07 华南理工大学 Preparation method of solid particle emulsified and stabilized papermaking sizing agent
CN111749046A (en) * 2019-08-29 2020-10-09 齐鲁工业大学 Alkyl ketene dimer sizing agent and preparation method and application thereof

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