CN103194934A - Preparation method of paper making sizing agent formed by emulsification of flaky solid particles - Google Patents

Preparation method of paper making sizing agent formed by emulsification of flaky solid particles Download PDF

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CN103194934A
CN103194934A CN2013101094995A CN201310109499A CN103194934A CN 103194934 A CN103194934 A CN 103194934A CN 2013101094995 A CN2013101094995 A CN 2013101094995A CN 201310109499 A CN201310109499 A CN 201310109499A CN 103194934 A CN103194934 A CN 103194934A
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preparation
solid particle
emulsification
bentonite
deionized water
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CN103194934B (en
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于得海
林兆云
李友明
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention discloses a preparation method of a paper making sizing agent formed by emulsification of flaky solid particles. The method comprises the following steps of: firstly, mixing a silane coupling agent with flaky nanometer bentonite solid particles and dispersing the mixture in deionized water; secondly, adding methylbenzene or absolute ethyl alcohol to prepare modified bentonite suspension liquid; thirdly, dispersing the flaky nanometer bentonite solid particles modified by the silane coupling agent into the deionized water, stirring uniformly, and regulating the pH value to 3.5-9.5; fourthly, mixing liquid paraffin with vinyl succinic anhydride and stirring uniformly to obtain mixed sizing oil liquid; and at last mixing the sizing oil liquid with the bentonite suspension liquid, wherein the paper making sizing agent with stably emulsified flaky solid particles is obtained after the mixture is emulsified. The paper making sizing gent has quite high stability, and the preparation method is simple, can be used for emulsifying the vinyl succinic anhydride into a stable emulsion without adding any surface active agent or high-molecular polyelectrolyte, also uses little emulsifying agent, is low in emulsification cost, and causes low pollution to the environment.

Description

A kind of preparation method of the glue used in paper-making by the emulsification of chip solid particle
Technical field
The present invention relates to the preparation method of glue used in paper-making, particularly the preparation method of the efficient glue used in paper-making of chip solid particle emulsification.
Background technology
Paper industry is copied the paper system by acidity and is turned to neutral and alkali to copy paper in recent years, is that the innovative of paper technology changes, and increases substantially paper quality expansion filler scope, reduces slurry consumption, energy consumption, has alleviated environmental pollution, has prolonged service life of equipment.Europe phase early 1980s with in, the cultural paper of alkaline bleach liquor sizing production accounts for 60%~65% of cultural paper total amount, enters the nineties up to 95%, in same period U.S.'s fine paper, the alkaline bleach liquor sizing ratio rises to more than 90% by 15%.China is from 1989, in having begun aborning to adopt, alkaline bleach liquor sizing, progressively popularizes in recent years, and based on alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA), big-and-middle-sized paper plant gradually adopts ASA at present., curing speed low owing to ASA sizing agent reactivity height, sizing material cost is widely used in fine paper and cardboard internal sizing soon, particularly is applicable to the applying glue of the large high-speed paper machine of coating in the machine.But ASA is a kind of papermaking neutral sizing agent of high reaction activity, hydrolysis rate is very fast, its emulsion is after the room temperature storage time surpasses 1 hour, sizing efficiency reduces, hydrolysate can cause the paper making obstacle and reduce applying glue efficient, therefore require it can be by quick emulsification when using ASA, the emulsion after the emulsification should be used as early as possible.And hydrolysis not only very easily takes place in alkenyl succinic anhydride (ASA), and alcoholysis, ammonia solution also very easily take place, so alcohols, carboxylic acids, ammoniac compounds should not be as the emulsifying agent of ASA.The emulsification of ASA sizing agent at present mainly is to utilize cationic starch and low-molecular-weight surfactant to come on-the-spot emulsification, and uses at once.Yet starch needs to re-use after first gelatinization, the cooling, makes the ASA emulsifying process rather complicated, wayward, and usually causes problems such as deposition, obstruction woollen blanket.Surfactant wherein also brings certain adverse effect to applying glue, and environment is also brought certain pollution.
Solid (particle) stable type emulsion, be commonly called the Pickering emulsion, it is a kind of traditional macromolecule organic surface active agent that do not need to add, and only with solia particle can stable emulsifying emulsion, the solia particle that is adsorbed in the oil-water interfaces place has high energy of adsorption E, make solia particle be difficult to break away from from oil-water interfaces again, can think that this mode by solia particle stable emulsifying emulsion is irreversible, and the Pickering emulsion has very strong stability, and present this emulsifying technology and research are widely used in every profession and trade and the field.Thereby the Pickering emulsion is owing to avoid using the macromolecule organic emulsifier can reduce the complexity of emulsifying process, improve the stability of emulsion and reduce the environmental pollution that caused by emulsifying agent etc. to denounce, and be a kind of New Emulsion that has potential using value.
Research and achievement that the emulsification of ASA sizing agent at present prepares the aspect also are enriched gradually.US Patent No. 6,346,554 have disclosed a kind of method of utilizing natural plant to stablize the ASA emulsion, it is said that natural plant gum can reach the efficient of executing that improves ASA at the more uniform film of fiber surface formation by improving retention, the hydrolysis of minimizing ASA and the deposition problems that thus cause of ASA on fiber.
US Patent No. 5,962,555 have disclosed the method that a kind of mixture that utilizes ionene polymer and polymine comes emulsification ASA, and ionene polymer wherein not only can improve the effect that applying glue efficient also has sterilization.Though having exempted starch gelatinization, these inventions give the inconvenience of bringing in the operation, yet, in order to obtain to stablize the ASA emulsion, still need to add the surfactant about 2%.
US Patent No. 6,284,099 has disclosed a kind of method of utilizing papermaking anionic microparticles retention agent such as bentonite, cataloid, organic fine particles and low quantity of surfactant and chelating agent to stablize the ASA emulsion, microparticle retention aid and sizing agent can be united two into one, simplify operation, reduced the consumption of surfactant.But still the adverse effect that can not avoid surfactant to bring fully, and the particulate constituent addition is excessive, and prepared ASA emulsion concentration is very low, is unfavorable for the storage of emulsion, and the ASA hydrolysis is serious.
Summary of the invention
The present invention is in order to overcome the deficiency of above technology, the invention provides a kind of preparation method of efficient glue used in paper-making of chip solid particle emulsification that any conventional surfactant and complex polyelectrolyte particle just can be emulsified into alkenyl succinic anhydride the emulsion of high stable that do not need to add.
The present invention is as emulsion solids particle emulsion stabilizer with silane coupler modified flake nano bentonite, atoleine is dispersed in the alkenyl succinic anhydride fluid, then silane coupler modified flake nano bentonite solid particle suspension is mixed with the mixed oil liquid of atoleine, alkenyl succinic anhydride, mixture is with the emulsification of high speed shear mulser, thereby makes the efficient glue used in paper-making by the emulsification of chip solid particle.
Purpose of the present invention specifically is achieved through the following technical solutions:
The preparation method of the glue used in paper-making of a kind of chip solid particle emulsification comprises the steps:
(1) preparation of nano modification bentonite solid particle: be that 25nm~300nm flake nano bentonite solid particle mixes with silane coupler and individual particle diameter, and be scattered in the deionized water, add toluene or absolute ethyl alcohol again, stirred 3~12 hours at 25 ℃~90 ℃ following constant temperature, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained is with toluene or ethanol cyclic washing 3~5 times; Again the back is ground in the decorating film oven dry and cross 200 mesh sieves, the gained residue on sieve is silane coupler modified flake nano bentonite solid particle; Described silane coupler is that carbon chain lengths is the alcoxyl fundamental mode silane coupler, dialkoxy fundamental mode silane coupler or the tri-alkoxy type silane coupler that contain four~dodecyl of C2~C12; The bentonitic mass ratio of described toluene or absolute ethyl alcohol and flake nano 20: 1~100: 1; The bentonitic mass ratio of described deionized water and flake nano is 4: 1~20: 1; Described silane coupler be flake nano bentonite solid particle quality 0.05%~50%;
(2) preparation of applying glue fluid: it is even that silane coupler modified flake nano bentonite solid particle is scattered in deionized water for stirring, obtains the bentonite mass percent and be 0.2%~8% water slurry, and regulate water slurry pH value to 3.5~9.5; Again with atoleine with stir after alkenyl succinic anhydride mixes, the applying glue fluid that obtains mixing, the mass percent of described atoleine in applying glue fluid is 10%~60%;
(3) preparation of glue used in paper-making: described applying glue fluid is mixed with the volume ratio of described bentonite water slurry according to 1: 7~3: 1, and mixture obtains the glue used in paper-making of chip solid particle stable emulsifying after emulsification.
For further realizing the object of the invention, the high speed shear mulser emulsification of the described mixture of step 3).The shear rate of described emulsification is 3000 rev/mins~20000 rev/mins, and the time is 2~10 minutes.The cation radical of described flake nano bentonite solid particle is sodium ion, calcium ion, magnesium ion, lithium ion or ammonium ion.Described deionized water is that resistance is greater than the deionized water of 18M Ω cm.Described alkenyl succinic anhydride (ASA) is 16 to the alkenyl succinic acid anhydride monomers of eicosyl, or contains 16 mixtures to the alkenyl succinic anhydride of eicosyl.Described silane coupler is γ-methacryloxypropyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-chloropropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxy oxosilane or methyl ethylene dimethoxy silane.Described pH value is by one or more adjustings in hydrochloric acid, acetic acid, uric acid and the citric acid.
Described atoleine is C16~C20 normal paraffin mixture, exists with liquid form under the normal temperature, and as preferably, the mass fraction of atoleine in applying glue fluid is 10%~60%.
Compared with prior art, the present invention has the following advantages:
(1) preparation method's emulsifying process of paper-making sizing agent emulsion of the present invention simply, does not need to add the emulsion that any conventional surfactant and complex polyelectrolyte particle just can be emulsified into ASA (alkenyl succinic anhydride) high stability;
(2) the flake nano modified cation chip solid particle of the Irreversible Adsorption that relates among the present invention can form the ASA stable emulsifying pik crop type emulsion, and this emulsion has high stability.Employed atoleine has the multiple action that reduces fluid polarity, assists emulsification, improves sizability.Preparation technology of the present invention is simple, do not need to add any surfactant and complex polyelectrolyte particle again and just alkenyl succinic anhydride can be emulsified into stable emulsion, and the emulsifying agent consumption is few, emulsification is with low cost, and environmental pollution is low.
The specific embodiment
Embodiment 1
With trialkoxy silane coupling agent (KH570, γ-methacryloxypropyl trimethoxy silane) be flake nano bentonite solid particle (the modification of sodium carbonate sodium bentonite of 25nm with particle diameter, original soil is taken from Zhejiang, provided by Sanding Sci. ﹠ Tech. Co., Ltd., Zhejiang) mix by 10% mass percent, add deionized water to mixture, the mass ratio of deionized water and flake nano bentonite solid particle is 10: 1, add toluene or absolute ethyl alcohol again, the mass ratio of deionized water and flake nano bentonite solid particle is 30: 1, under 75 ℃, added thermal agitation 6 hours, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained toluene cyclic washing.Decorating film oven dry after the washing is ground the back and is crossed 200 mesh sieves, gained residue on sieve (residue in the non-sieve) is scattered in the deionized water (resistance is greater than 18M Ω cm), stir, obtain flake nano modified alta-mud mass fraction and be 1% water slurry, regulate water slurry pH value to 6 with the hydrochloric acid of 0.1mol/L, obtain good dispersion after stirring, do not have the flake nano modified alta-mud solid particle water slurry that precipitates.
Atoleine is mixed with the cetyl alkenyl succinic anhydride, stir, obtain the atoleine mass fraction and be 30% mixing application fluid.Again flake nano modified alta-mud solid particle water slurry is mixed according to 1: 1 volume ratio with mixing application fluid, mixture high speed shear mulser (FLUKO/FA35 high speed shear mulser, Shanghai Frock Fluid Machinery Manufacture Co., Ltd.) emulsification 3 minutes under 6000 rev/mins shear rate makes the milky efficient paper-making sizing agent emulsion by the emulsification of chip solid particle of homogeneous.The emulsion droplet particle mean size is 4.5 μ m, 5 minutes no changes of emulsion centrifugal under centrifuge (4000 rev/mins of rotating speeds), and no phase body is separated out, no demulsifying phenomenon, emulsion was placed after 1 day does not have significant change, and stability of emulsion is good.Its main stable mechanism is to utilize the nano-sheet solid particle at the formed solid particle interfacial film of the Irreversible Adsorption at oil-water interfaces place; play the effect that intercepts and protect emulsion droplet; thereby the ASA stable emulsifying is formed pik crop type emulsion, and this emulsion has high stability.Wherein atoleine has the multiple action that reduces fluid polarity, assists emulsification, improves sizability.
Prepared sizing agent emulsion is carried out plasm-glue-blending, copy paper with the square handshcet former of laboratory PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m 2Slurry is 100% hardwood pulp, alkenyl succinic anhydride consumption 0.15% (to the mass percent of oven dry stock), cationic polyacrylamide (CPAM, molecular weight 8,000,000, Ciba provides) consumption 0.03% (to the oven dry stock mass percent), addition of aluminum sulfate 1% (to the oven dry stock mass percent).Recording the page degree of sizing is 132 seconds (degree of sizing is measured according to GB/T5405-2002), and the paper sizing degree is good.Preparation method's emulsifying process of prepared pickering emulsion type paper-making sizing agent emulsion simply, does not need to add the emulsion that any conventional surfactant and complex polyelectrolyte particle just can be emulsified into ASA (alkenyl succinic anhydride) high stable, can effectively reduce production costs, improve problems such as environmental pollution.
Embodiment 2
With trialkoxy silane coupling agent (KH550, γ-chloropropyl triethoxysilane) be flake nano bentonite solid particle (the calcium carbonate modified calcium-base bentonite of 50nm with particle diameter, original soil is taken from Zhejiang, provided by Sanding Sci. ﹠ Tech. Co., Ltd., Zhejiang) mix by 5% mass percent, add deionized water to mixture, the deionized water consumption is 20: 1 with respect to the mass ratio of bentonite solid particle, add toluene or absolute ethyl alcohol again, consumption is 60: 1 with respect to the mass ratio of bentonite solid particle, under 75 ℃, added thermal agitation 8 hours, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained is with toluene or ethanol cyclic washing.Decorating film oven dry after the washing is ground the back and is crossed 200 mesh sieves, the gained residue on sieve is scattered in the deionized water, stir, obtain flake nano modified alta-mud mass fraction and be 5% water slurry, regulate water slurry pH value to 7 with the acetum of 0.1mol/L, obtain good dispersion after stirring, do not have the flake nano modified alta-mud solid particle water slurry that precipitates.
Atoleine is mixed with the octadecyl alkenyl succinic anhydride, stir, obtain the atoleine mass fraction and be 20% mixing application fluid.Flake nano modified alta-mud solid particle water slurry is mixed according to 1: 3 volume ratio with mixing application fluid, mixture high speed shear mulser (FLUKO/FA25 high speed shear mulser, Shanghai Frock Fluid Machinery Manufacture Co., Ltd.) emulsification 5 minutes under 8000 rev/mins shear rate makes the milky efficient paper-making sizing agent emulsion by the emulsification of chip solid particle of homogeneous.The emulsion droplet particle mean size is 4.2 μ m, 10 minutes no changes of emulsion centrifugal under centrifuge (4000 rev/mins of rotating speeds), and no phase body is separated out, no demulsifying phenomenon, emulsion was placed after 1 day does not have significant change, and the gained stability of emulsion is good.
Prepared sizing agent emulsion is carried out plasm-glue-blending, copy paper with the square handshcet former of laboratory PTI, page is dried in FI119 type electrothermal drying cylinder, and page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m 2Slurry is 100% hardwood pulp, alkenyl succinic anhydride consumption 0.2% (to the mass percent of oven dry stock), cationic polyacrylamide (CPAM, molecular weight 8,000,000, Ciba provides) consumption 0.03% (to the mass percent of oven dry stock), addition of aluminum sulfate 1% (to the mass percent of oven dry stock).Recording the page degree of sizing is 212 seconds (degree of sizing is measured according to GB/T5405-2002), and the paper sizing degree is good.
Embodiment 3
With trialkoxy silane coupling agent (KH560, γ-glycidyl ether oxygen propyl trimethoxy silicane) and particle diameter be 100nm the flake nano bentonite (magnesium base modified alta-mud, original soil is taken from Liaoning, by The Chaoyang is moistened eastern produce and is sold Co., LtdProviding) solid particle mixes by 2% mass percent, add deionized water to mixture, the deionized water consumption is 15: 1 with respect to the mass ratio of bentonite solid particle, add toluene or absolute ethyl alcohol again, consumption is 50: 1 with respect to the mass ratio of bentonite solid particle, adds thermal agitation 5 hours under 75 ℃, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained is with toluene or ethanol cyclic washing.Decorating film oven dry after the washing is ground the back and is crossed 200 mesh sieves, the gained residue on sieve is scattered in the deionized water, stir, obtain flake nano modified alta-mud mass fraction and be 5% water slurry, regulate water slurry pH value to 5 with the citric acid solution of 0.1mol/L, obtain good dispersion after stirring, do not have the flake nano modified alta-mud solid particle water slurry that precipitates.
Atoleine is mixed with the eicosyl alkenyl succinic anhydride, stir, obtain the atoleine mass fraction and be 50% mixing application fluid.Flake nano modified alta-mud solid particle water slurry is mixed according to 2: 1 volume ratios with mixing application fluid, mixture high speed shear mulser (FLUKO/FM200 high speed shear mulser, Shanghai Frock Fluid Machinery Manufacture Co., Ltd.) emulsification 7 minutes under 10000 rev/mins shear rate makes the milky efficient paper-making sizing agent emulsion by the emulsification of chip solid particle of homogeneous.The emulsion droplet particle mean size is 5 μ m, 10 minutes no changes of emulsion centrifugal under centrifuge (4000 rev/mins of rotating speeds), and no phase body is separated out, no demulsifying phenomenon, emulsion was placed after 1 day does not have significant change, and stability of emulsion is good.
Prepared sizing agent emulsion is carried out plasm-glue-blending, copy paper with the square handshcet former of laboratory PTI, page is dried in FI119 type electrothermal drying cylinder, and page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m2.Slurry is 100% hardwood pulp, alkenyl succinic anhydride consumption 0.5% (to the mass percent of oven dry stock), cationic polyacrylamide (CPAM, molecular weight 8,000,000, Ciba provides) consumption 0.03% (to the mass percent of oven dry stock), addition of aluminum sulfate 1% (to the mass percent of oven dry stock).Recorded the page degree of sizing 278 seconds (degree of sizing is measured according to GB/T5405-2002), the paper sizing degree is good.
Embodiment 4
With dialkoxy silicane coupling agent (KH161, methyl ethylene dimethoxy silane) be flake nano bentonite (the ammonium organobentonite of 50nm with particle diameter, original soil is taken from Zhejiang, being provided by Sanding Sci. ﹠ Tech. Co., Ltd., Zhejiang) solid particle mixes by 8% mass percent, add deionized water to mixture, the deionized water consumption is 20: 1 with respect to the mass ratio of bentonite solid particle, add toluene or absolute ethyl alcohol again, consumption is 60: 1 with respect to the mass ratio of bentonite solid particle, under 75 ℃, added thermal agitation 6 hours, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained is with toluene or ethanol cyclic washing.Decorating film oven dry after the washing is ground the back and is crossed 200 mesh sieves, the gained residue on sieve is scattered in the deionized water, stir, obtain flake nano modified alta-mud mass fraction and be 3% water slurry, regulate water slurry pH value to 6 with the uric acid solution of 0.5mol/L, obtain good dispersion after stirring, do not have the flake nano modified alta-mud solid particle water slurry that precipitates.
With atoleine and 16~eicosyl alkenyl succinic anhydride (by percentage to the quality, it is by 15% cetyl alkenyl succinic anhydride, 10% heptadecyl alkenyl succinic anhydride, 45% octadecyl alkenyl succinic anhydride, 5% nonadecyl alkenyl succinic anhydride, 25% eicosyl alkenyl succinic anhydride is formed) mix, stir, obtain the atoleine mass fraction and be 40% mixing application fluid.Flake nano modified alta-mud solid particle water slurry is mixed according to 1: 7 volume ratio with mixing application fluid, mixture high speed shear mulser (FLUKO/FA25 high speed shear mulser, Shanghai Frock Fluid Machinery Manufacture Co., Ltd.) emulsification 5 minutes under 15000 rev/mins shear rate makes the milky efficient paper-making sizing agent emulsion by the emulsification of chip solid particle of homogeneous.The emulsion droplet particle mean size is 3.5 μ m, 10 minutes no changes of emulsion centrifugal under centrifuge (4000 rev/mins of rotating speeds), and no phase body is separated out, no demulsifying phenomenon, emulsion was placed after 1 day does not have significant change, and stability of emulsion is good.
Prepared sizing agent emulsion is carried out plasm-glue-blending, copy paper with the square handshcet former of laboratory PTI, page is dried in FI119 type electrothermal drying cylinder, and page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m 2Slurry is 100% hardwood pulp, alkenyl succinic anhydride consumption 0.2% (to the mass percent of oven dry stock), cationic polyacrylamide (CPAM, molecular weight 8,000,000, Ciba provides) consumption 0.03% (to the mass percent of oven dry stock), addition of aluminum sulfate 1% (to the mass percent of oven dry stock).Recording the page degree of sizing is 334 seconds (degree of sizing is measured according to GB/T5405-2002), and the paper sizing degree is good.
Embodiment 5
With dialkoxy silicane coupling agent (KH602, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxy oxosilane) be flake nano bentonite (the hectorite bentonite of 25nm with particle diameter, river, Shanghai Lay bio tech ltd provides) solid particle mixes by 15% mass percent, add deionized water to mixture, the deionized water consumption is 25: 1 with respect to the mass ratio of bentonite solid particle, add toluene or absolute ethyl alcohol again, consumption is 70: 1 with respect to the mass ratio of bentonite solid particle, under 75 ℃, added thermal agitation 5 hours, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained is with toluene or ethanol cyclic washing.Decorating film oven dry after the washing is ground the back and is crossed 200 mesh sieves, the gained residue on sieve is scattered in the deionized water, stir, obtain flake nano modified alta-mud mass fraction and be 2% water slurry, regulate water slurry pH value to 4.5 with the hydrochloric acid of 0.1mol/L, obtain good dispersion after stirring, do not have the flake nano modified alta-mud solid particle water slurry that precipitates.
With atoleine and 16,18, eicosyl alkenyl succinic anhydride (by percentage to the quality, it is by 15% hexadecylene base succinyl oxide, 75% octadecylene base succinyl oxide, 10% icosa alkene base succinyl oxide is formed) mix, stir, obtain the atoleine mass fraction and be 20% mixing application fluid.Flake nano modified alta-mud solid particle water slurry is mixed according to 4: 5 volume ratios with mixing application fluid, mixture high speed shear mulser (FLUKO/FA35 high speed shear mulser, Shanghai Frock Fluid Machinery Manufacture Co., Ltd.) emulsification 5 minutes under 6000 rev/mins shear rate makes the milky efficient paper-making sizing agent emulsion by the emulsification of chip solid particle of homogeneous.The emulsion droplet particle mean size is 3 μ m, 10 minutes no changes of emulsion centrifugal under centrifuge (4000 rev/mins of rotating speeds), and no phase body is separated out, no demulsifying phenomenon, emulsion was placed after 1 day does not have significant change, and stability of emulsion is good.Main stable emulsifying mechanism is to utilize the cation nanometer solid particle at the formed solid particle interfacial film of the Irreversible Adsorption at oil-water interfaces place, intercepts and the protection emulsion droplet, thereby the ASA stable emulsifying is formed the pik crop type emulsion with superregulated property.Wherein atoleine has the multiple action that reduces fluid polarity, assists emulsification, improves sizability.
Prepared sizing agent emulsion is carried out plasm-glue-blending, copy paper with the square handshcet former of laboratory PTI, page is dried in FI119 type electrothermal drying cylinder, and page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m 2Slurry is 100% hardwood pulp, alkenyl succinic anhydride consumption 0.5% (to the mass percent of oven dry stock), cationic polyacrylamide (CPAM, molecular weight 8,000,000, Ciba provides) consumption 0.03% (to the mass percent of oven dry stock), addition of aluminum sulfate 1% (to the mass percent of oven dry stock).Recording the page degree of sizing is 378 seconds (degree of sizing is measured according to GB/T5405-2002), and the paper sizing degree is good.Preparation method's emulsifying process of prepared pickering emulsion type paper-making sizing agent emulsion simply, does not need to add the emulsion that any conventional surfactant and complex polyelectrolyte particle just can be emulsified into ASA (alkenyl succinic anhydride) high stable, and effectively reduce production costs, improve the problems such as discharging of pollutant.

Claims (8)

1. the preparation method of the glue used in paper-making of chip solid particle emulsification is characterized in that comprising the steps:
(1) preparation of nano modification bentonite solid particle: be that the flake nano bentonite solid particle of 25nm~300nm mixes with silane coupler and individual particle diameter, and be scattered in the deionized water, add toluene or absolute ethyl alcohol again, stirred 3~12 hours at 25 ℃~90 ℃ following constant temperature, leave standstill and be cooled to room temperature, obtain modified alta-mud suspension, extracting gained suspension then, the decorating film of extracting gained is with toluene or ethanol cyclic washing 3~5 times; Again the back is ground in the decorating film oven dry and cross 200 mesh sieves, the gained residue on sieve is silane coupler modified flake nano bentonite solid particle; Described silane coupler is that carbon chain lengths is the alcoxyl fundamental mode silane coupler, dialkoxy fundamental mode silane coupler or the tri-alkoxy type silane coupler that contain four~dodecyl of C2~C12; The bentonitic mass ratio of described toluene or absolute ethyl alcohol and flake nano 20: 1~100: 1; The bentonitic mass ratio of described deionized water and flake nano is 4: 1~20: 1; Described silane coupler be flake nano bentonite solid particle quality 0.05%~50%;
(2) preparation of applying glue fluid: it is even that silane coupler modified flake nano bentonite solid particle is scattered in deionized water for stirring, obtains the bentonite mass percent and be 0.2%~8% water slurry, and regulate water slurry pH value to 3.5~9.5; Again with atoleine with stir after alkenyl succinic anhydride mixes, the applying glue fluid that obtains mixing, the mass percent of described atoleine in applying glue fluid is 10%~60%;
(3) preparation of glue used in paper-making: described applying glue fluid is mixed with the volume ratio of described bentonite water slurry according to 1: 7~3: 1, and mixture obtains the glue used in paper-making of chip solid particle stable emulsifying after emulsification.
2. preparation method according to claim 1 is characterized in that: the high speed shear mulser emulsification of the described mixture of step 3).
3. preparation method according to claim 2, it is characterized in that: the shear rate of described emulsification is 3000 rev/mins~20000 rev/mins, and the time is 2~10 minutes.
4. preparation method according to claim 1, it is characterized in that: the cation radical of described flake nano bentonite solid particle is sodium ion, calcium ion, magnesium ion, lithium ion or ammonium ion.
5. preparation method according to claim 1, it is characterized in that: described deionized water is that resistance is greater than the deionized water of 18M Ω cm.
6. preparation method according to claim 1 is characterized in that: described alkenyl succinic anhydride is the 16 alkenyl succinic acid anhydride monomers to eicosyl, or contains 16 mixtures to the alkenyl succinic anhydride of eicosyl.
7. preparation method according to claim 1, it is characterized in that: described silane coupler is γ-methacryloxypropyl trimethoxy silane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-chloropropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxy oxosilane or methyl ethylene dimethoxy silane.
8. preparation method according to claim 1 is characterized in that: described pH value is by one or more adjustings in hydrochloric acid, acetic acid, uric acid and the citric acid.
CN201310109499.5A 2013-03-29 2013-03-29 A kind of preparation method by the glue used in paper-making of chip solid particle emulsification Expired - Fee Related CN103194934B (en)

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CN112796157A (en) * 2021-01-12 2021-05-14 齐鲁工业大学 AKD/ASA composite papermaking sizing agent and preparation method and application thereof
CN113481736A (en) * 2021-08-12 2021-10-08 安徽高梵电子商务有限公司 Waterproof spraying liquid for down jackets and preparation method thereof
CN114395387A (en) * 2022-03-15 2022-04-26 西南石油大学 Water-in-oil in-situ emulsified nano oil displacement agent with high phase transition point and application thereof
CN116042041A (en) * 2023-03-07 2023-05-02 江苏艾肯复元新材料技术有限公司 Thermochromic water-based nano coating and preparation method thereof
CN116676808A (en) * 2023-04-24 2023-09-01 山东奥赛新材料有限公司 ASA sizing agent, preparation method and application thereof

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CN106087560A (en) * 2016-06-28 2016-11-09 安阳华森纸业有限责任公司 Fluorine silicon resin and the preparation method of Nanocomposites modified paraffin waterproofing agent
CN112796157A (en) * 2021-01-12 2021-05-14 齐鲁工业大学 AKD/ASA composite papermaking sizing agent and preparation method and application thereof
CN113481736A (en) * 2021-08-12 2021-10-08 安徽高梵电子商务有限公司 Waterproof spraying liquid for down jackets and preparation method thereof
CN114395387A (en) * 2022-03-15 2022-04-26 西南石油大学 Water-in-oil in-situ emulsified nano oil displacement agent with high phase transition point and application thereof
CN114395387B (en) * 2022-03-15 2022-12-20 西南石油大学 Water-in-oil in-situ emulsified nano oil displacement agent with high phase transition point and application thereof
CN116042041A (en) * 2023-03-07 2023-05-02 江苏艾肯复元新材料技术有限公司 Thermochromic water-based nano coating and preparation method thereof
CN116042041B (en) * 2023-03-07 2023-11-10 江苏艾肯复元新材料技术有限公司 Thermochromic water-based nano coating and preparation method thereof
CN116676808A (en) * 2023-04-24 2023-09-01 山东奥赛新材料有限公司 ASA sizing agent, preparation method and application thereof

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