CN101574834B - Method for preparing high-stabliliy ASA papermaking sizing agent emulsion - Google Patents
Method for preparing high-stabliliy ASA papermaking sizing agent emulsion Download PDFInfo
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- CN101574834B CN101574834B CN2009100204474A CN200910020447A CN101574834B CN 101574834 B CN101574834 B CN 101574834B CN 2009100204474 A CN2009100204474 A CN 2009100204474A CN 200910020447 A CN200910020447 A CN 200910020447A CN 101574834 B CN101574834 B CN 101574834B
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Abstract
The invention relates to a method for preparing a high-stabliliy ASA papermaking sizing agent emulsion, which comprises the following steps that: smectite is dispersed in water to form a suspension; the suspension is mixed with oleosus ASA under the action of mechanical agitation to prepare a stable smectite ASA emulsion; and then a chitosan solution dissolved in dilute acid is added in the emulsion; and then a weak alkali is added to form the stable O/W type ASA emulsion under the action of the mechanical agitation. The method has the advantages that: the preparation process is simple; emulsifier dosage is less; surfactant addition is adovided; and the made ASA latices has high stability, short bubble diameter and high gluing efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of ASA papermaking sizing agent emulsion of high stability, be specifically related to a kind of natural polymers that utilizes and adjust the relative wettability energy of montmorillonite particulate ASA and water, improve emulsification and the stabilization of solia particle, with the ASA emulsion of preparation high stability and high applying glue efficient to ASA.
Background technology
ASA (alkenyl succinic anhydride) is a kind of papermaking neutral sizing agent of high reaction activity, advantage such as have that applying glue efficient height, curing speed are fast, applying glue pH value wide accommodation, one-tenth paper are non-slip, be widely used in the plasm-glue-blending of fine paper and cardboard, the large high-speed paper machine that is particularly useful for coating in the machine, the consumption that help to improve applying glue efficient, reduces glue used in paper-making.Yet, the ASA facile hydrolysis, hydrolysis not only reduces applying glue efficient, and hydrolysate also can cause the obstacle of manufacturing paper with pulp of paper, need be in the on-the-spot emulsification of machine room.Mainly utilize cationic starch and low-molecular-weight surfactant to come emulsification ASA at present.Because starch needs to re-use after gelatinization, cooling earlier, the emulsifying process complexity is wayward, and the key of ASA emulsification to be paper industry make good use of ASA.Therefore, the emulsification method of the ASA of more easy, the easy row of development and to improve emulsification system be the important channel that paper industry improves ASA applying glue efficient to the emulsifiability of ASA.
U.S. Pat 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.U.S. Pat 6,346,554 have disclosed a kind of method of utilizing natural plant to come emulsification ASA, 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.Though having exempted starch gelatinization, these inventions give the inconvenience that brings in the operation, yet, in order to obtain more stable ASA emulsion, still need to add the surfactant about 2%, and the consumption of emulsifying agent is too high, often be 1～4 times of ASA.
" Chinese papermaking " the 1st phase in 2007 article of the 11st page has reported to utilize to have the method for surface-active synthetic high polymer emulsifying agent emulsification ASA, is 1: 1 amount but need mass ratio with ASA at least, could obtain the ASA emulsion of suitable applying glue efficient; The 22nd page of " Chinese paper industry " the 4th phase in 2009 reported the technology of utilizing benzene emulsion copolymer emulsification ASA, the mass fraction of emulsifying agent can be reduced to 20%, but need adapted retention agent and stabilizing agent could obtain stable preferably and sizing efficiency, the inventory of emulsification ASA required input is still very high.
U.S. Pat 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 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.Publication number is that the Chinese patent of CN101333789 discloses a kind of bentonite and hydrotalcite of utilizing and unites use, the method that is used for emulsification and stable ASA, this emulsifying process can avoid using surfactant and fully thus to the adverse effect of ASA applying glue, and preparation technology is simple, the emulsifying agent consumption is few, emulsification is with low cost, and prepared emulsion concentration height, hydrolytic stability is good, applying glue efficient is higher.Yet, poly-effect is equivalent to improve bentonitic granularity because hydrotalcite is to bentonitic little wadding, generally stable than the montmorillonite emulsion liquid-drop diameter of prepared ASA emulsion liquid-drop diameter is big, if think further to improve the applying glue efficient of ASA, then needs to seek in addition his footpath.
Summary of the invention
For solving the problem of above-mentioned existence, the invention provides a kind of preparation method of ASA papermaking sizing agent emulsion of high stability.Not only the emulsifying agent consumption is few for this method, emulsifying process does not use surfactant simply, fully, and the applying glue efficient of gained emulsion can be greatly improved.
The present invention is achieved by the following technical solutions:
Scheme one: montmorillonite is dispersed in the water, under mechanical agitation, it is mixed with oily ASA,, prepare the stable O/W type ASA emulsion of montmorillonite through the shearing peptizaiton of certain hour; The chitosan solution that adds the diluted acid dissolving then earlier adds weak base again to above-mentioned ASA emulsion, shitosan is deposited to stablize on the montmorillonite of ASA emulsion, again through suitable mechanical agitation, prepares stable O/W type ASA emulsion.
For simplifying the operation, also can adopt scheme two: the chitosan solution of montmorillonite, weak base and diluted acid dissolving is dispersed in the water jointly, the shitosan through the acid dissolving is deposited on the montmorillonite through weak base earlier, make through the deposition modified montmorillonite particulate emulsifying agent of shitosan; Under mechanical agitation, mentioned emulsifier is mixed with the ASA of oily again,, prepare stable O/W type ASA emulsion through the shearing peptizaiton of certain hour.
ASA sizing agent involved in the present invention is the various ASA industrial products that are used for paper-making sizing without emulsification that exist with liquid form under the normal temperature, in order to improve applying glue efficient, preferably do not add the ASA industrial products of surfactant, itself and the mass ratio of Total Water that constitutes ASA emulsion are generally between 1: 1～4, preferred ratio is 1: 2～3, the Total Water of formation ASA emulsion refers to be added at last all water yields among the ASA, comprises all water yields of disperseing montmorillonite, dissolving shitosan and ammoniacal liquor.
Montmorillonite involved in the present invention is bentonitic essential mineral composition, can be by natural sodium bentonite, through the calcium-base bentonite of sodium modification or through the acquisition of purifying of the neutral sodium-ionized bentonite of sodium fluoride, natrium citricum modification, the content of montmorillonite is greater than 90%.Montmorillonite is very strong to the affinity of water, in water through the peelable flakiness shape of suitable shear action, the thickness of its single sheet is less than 1nm, in the present invention as the main body emulsifying agent for preparing ASA emulsion, the mass ratio of montmorillonite and ASA sizing agent is 1: 5～25, and preferred ratio is 1: 10～20.
The natural polymer that contains primary amino radical involved in the present invention is a shitosan, and in order to improve the solubility property of shitosan, the deacetylation that requires shitosan is greater than 85%, and viscosity is less than 1000mPas, preferably less than 750mPas.The mass ratio of shitosan and ASA generally is controlled in 1: 100～2000 the scope, and the most frequently used mass ratio is 1: 200～800.
The diluted acid of dissolving shitosan involved in the present invention is generally acetic acid or hydrochloric acid, preferred acetic acid.The mass ratio of diluted acid and shitosan is generally 1: 0.1～1.
The weak base of deposition shitosan involved in the present invention is generally ammoniacal liquor, strong base-weak acid salt such as sodium carbonate, sodium bicarbonate etc., preferred ammoniacal liquor.The mass ratio of weak base and shitosan generally is controlled at 2～20: 1, and more preferred ratio is 5～10: 1.
In scheme one, montmorillonite suspension was added to ASA in the montmorillonite suspension under stirring action with both mixing of ASA, also montmorillonite suspension is under agitation joined among the ASA of oily, but preferably montmorillonite suspension is joined among the ASA of oily; Mechanical agitation can be provided by any mixing plant or mechanical shearing equipment, require mixing speed between 2000～12000 rev/mins, preferably be controlled between 5000～10000 rev/mins, mixing time 2～15 minutes, preferred scheme is 3～10 minutes, and the ASA that thinks oily is dispersed into emulsion comparatively equably in water provide enough energy.In the mixing of the ASA emulsion that related shitosan with the diluted acid dissolving, ammoniacal liquor and montmorillonite are stable, need suitable mechanical agitation equally, mixing speed is 2000～12000 rev/mins, and preferably scheme is 5000～10000 rev/mins; Mixing time was controlled at 2～15 minutes, and preferred scheme is to be controlled at 3～10 minutes.
In scheme two, related shitosan, montmorillonite and weak base with the diluted acid dissolving are dispersed in the water jointly, are meant shitosan is dissolved in earlier in the diluted acid, obtain sour molten shitosan, are dispersed in the water with montmorillonite and weak base again.Both can earlier montmorillonite be dispersed in the water,, under stirring action, add sour molten shitosan, weak base more successively through suitable mechanical agitation or shear action; Also montmorillonite directly can be dispersed in the sour molten shitosan, effect under agitation adds weak base down again; Also montmorillonite can be dispersed in the weak base, under agitation mix again with the molten shitosan of acid; But more preferred scheme is that montmorillonite is dispersed in the water, through suitable mechanical shearing effect, under agitation adds sour molten shitosan and weak base more successively, prepares the deposition modified montmorillonite particulate emulsifying agent of shitosan.
Related mechanical agitation is meant the stirring action by 500～2000 rev/mins of any mechanical agitation or rotating speeds that shearing equipment provided, mixing time 1～30 minute in shitosan, montmorillonite and the weak base process of the dissolving of above-mentioned dispersion diluted acid.
The deposition modified montmorillonite particulate emulsifying agent of related shitosan mixes with ASA's, and is similar with mixing of montmorillonite suspension and ASA.The deposition modified montmorillonite particulate emulsifying agent of shitosan was added to ASA in the deposition modified montmorillonite particulate emulsifying agent of shitosan under stirring action with both mixing of ASA, also the montmorillonite particulate emulsifying agent that shitosan is deposition modified under agitation joins among the ASA of oily, joins among the ASA of oily but more preferred scheme is the montmorillonite particulate emulsifying agent that shitosan is deposition modified.
In the mixed process of deposition modified montmorillonite particulate emulsifying agent of shitosan involved in the present invention and ASA, mechanical agitation can be provided by any mixing plant or mechanical shearing equipment, general control mixing speed is at 2000～12000 rev/mins, preferably be controlled between 5000～10000 rev/mins, mixing time 2～15 minutes, preferred scheme are 3～10 minutes.
The invention has the beneficial effects as follows: preparation technology is simple, the emulsifying agent consumption is few, do not need to add any surfactant, and prepared ASA emulsion stability is good, liquid-drop diameter is little, applying glue efficient height.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, do not constitute any limitation of the invention.Remove other and indicate, all umbers among the embodiment all by weight.
Embodiment 1
The shitosan of 0.01 part of deacetylation 90.2%, viscosity 60mPas is dissolved in 2 parts of deionized waters that contain 0.02 part of acetate, obtains sour molten shitosan; It is standby to prepare 3 parts of ammoniacal liquor that contain 0.1 part of ammonia in addition.
0.8 part of montmorillonite that obtains through the sodium-ionized bentonite purification of natrium citricum modification is scattered in 20 parts of water, after 500 rev/mins mixing speeds stir 30 minutes, add among the ASA of 20 parts of oilies, under 12000 rev/mins mixing speed, stirred 2 minutes, obtain the stable ASA emulsion of montmorillonite; Afterwards again under 12000 rev/mins mixing speed, the sour molten shitosan that adds above-mentioned preparation, stir after 2 minutes, add the ammoniacal liquor of above-mentioned preparation, continue to stir 2 minutes, obtain milky O/W type ASA emulsion, the mass percent of ASA is about 44%, and emulsion pH value is about 7, and the liquid-drop diameter of emulsion is 1～2 μ m, emulsion centrifugal 10 minutes through 4000 rev/mins rotating speed is not seen variation.
Get 100 parts of hardwood pulps and be dispersed in 9900 parts of water, after being uniformly dispersed, add 1.5 parts of above-mentioned ASA emulsions, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 74s.
Embodiment 2
The shitosan of 0.02 part of deacetylation 90.2%, viscosity 60mPas is dissolved in 2 parts of deionized waters that contain 0.02 part of acetate, obtains sour molten shitosan; Prepare 3 parts of ammoniacal liquor that contain 0.1 part of ammonia in addition.The sodium-ionized bentonite of the 0.8 part of natrium citricum modification montmorillonite that obtains of purifying is scattered in 15 parts of water, stirred 1 minute, obtain montmorillonite suspension through 2000 rev/mins mixing speeds.In montmorillonite suspension, add the above-mentioned sour molten shitosan and the ammoniacal liquor of preparation in advance successively, and stirred 1 minute down at 2000 rev/mins respectively, obtain the deposition modified montmorillonite suspension of shitosan.
Take by weighing oily ASA20 part, the deposition modified montmorillonite suspension of shitosan that adds above-mentioned preparation, stirring and emulsifying is 10 minutes under 8000 rev/mins rotating speed, make milky O/W type ASA emulsion, emulsion pH value is about 7, and the mass percent of ASA is about 50%, emulsion liquid-drop diameter 1～2 μ m, emulsion descended centrifugal 10 minutes at 4000 rev/mins through centrifuge, did not see variation.
Get 100 parts of hardwood pulps and be dispersed in 9900 parts of water, after being uniformly dispersed, add 1 part of above-mentioned ASA emulsion liquid, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 65s.
Embodiment 3
The shitosan of 0.025 part of deacetylation 86.7%, viscosity 60mPas is dissolved in 5 parts of deionized waters that contain 0.05 part of acetate, obtains sour molten shitosan; It is standby to prepare 5 parts of ammoniacal liquor that contain 0.2 part of ammonia in addition.
1.5 parts of montmorillonites that obtain through the sodium-ionized bentonites purification of sodium fluoride modification are scattered in 30 parts of water, after 1000 rev/mins mixing speeds are disperseed 1 minute, add among the ASA of 20 parts of oilies, under 10000 rev/mins mixing speed, stirred 2 minutes, obtain the stable ASA emulsion of montmorillonite; Afterwards again under 10000 rev/mins mixing speed, the sour molten shitosan that adds above-mentioned preparation, stir after 2 minutes, add the ammoniacal liquor of above-mentioned preparation, continue to stir 2 minutes, obtain milky O/W type ASA emulsion, the mass percent of ASA is about 33%, and emulsion pH value is about 7, and the liquid-drop diameter of emulsion is about 1 μ m, emulsion centrifugal 10 minutes through 4000 rev/mins rotating speed is not seen variation.
Get 100 parts of softwood pulps and be dispersed in 9900 parts of water, after being uniformly dispersed, add 2 parts of above-mentioned ASA emulsions, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 97s.
Embodiment 4
The shitosan of 0.1 part of deacetylation 90.2%, viscosity 60mPas is dissolved in 10 parts of deionized waters that contain 0.2 part of acetate, obtains sour molten shitosan; It is standby to prepare 10 parts of ammoniacal liquor that contain 0.5 part of ammonia in addition.
2 parts of montmorillonites that obtain through the sodium-ionized bentonites purification of sodium fluoride modification are scattered in 20 parts of water, disperseed 2 minutes, obtain montmorillonite suspension through 1000 rev/mins mixing speeds.In montmorillonite suspension, add the above-mentioned sour molten shitosan of preparation in advance, stirred 30 minutes down, add the ammoniacal liquor of above-mentioned preparation, continue to stir 30 minutes down, obtain the deposition modified montmorillonite suspension of shitosan at 500 rev/mins at 500 rev/mins.
Take by weighing oily ASA10 part, add in the deposition modified montmorillonite suspension of the shitosan of above-mentioned preparation, stirring and emulsifying is 10 minutes under 5000 rev/mins rotating speed.Make milky O/W type ASA emulsion, emulsion pH value is about 7, and the mass percent of ASA is about 20%, and about emulsion liquid-drop diameter 2～4 μ m, emulsion descended centrifugal 10 minutes at 3000 rev/mins through centrifuge, did not see layering.
Get 50 parts of hardwood pulps and 50 parts of Straw Pulp are dispersed in 9900 parts of water, after being uniformly dispersed, add 2.5 parts of above-mentioned ASA emulsion liquid, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 47s.
Embodiment 5
The shitosan of 0.01 part of deacetylation 90.2%, viscosity 60mPas is dissolved in 10 parts of deionized waters that contain 0.1 part of HCl, obtains sour molten shitosan; Prepare 5 parts in addition and contain 0.1 part of Na
2CO
3Sodium carbonate liquor standby.
1.5 parts of montmorillonites that obtain through the purification of sodium fluoride modified alta-mud are scattered in 25 parts of water, disperseed 2 minutes, obtain montmorillonite suspension through 1000 rev/mins mixing speeds.In montmorillonite suspension, add the above-mentioned sour molten shitosan of preparation in advance, stirred 5 minutes down, add the sodium carbonate liquor of above-mentioned preparation, continue to stir 5 minutes down, obtain the deposition modified montmorillonite suspension of shitosan at 1000 rev/mins at 1000 rev/mins.
The montmorillonite suspension that the shitosan of above-mentioned preparation is deposition modified adds among 20 parts of oily ASA, and stirring and emulsifying is 5 minutes under 8000 rev/mins rotating speed.Make milky O/W type ASA emulsion, emulsion pH value is about 7, and the mass percent of ASA is about 33%, and about emulsion liquid-drop diameter 2～4 μ m, emulsion descended centrifugal 10 minutes at 3000 rev/mins through centrifuge, did not see layering.
Get 100 parts of Straw Pulp and be dispersed in 9900 parts of water, after being uniformly dispersed, add 2 parts of above-mentioned ASA emulsion liquid, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 43s.
Embodiment 6
The shitosan of 0.05 part of deacetylation 90.2%, viscosity 60mPas is dissolved in 5 parts of deionized waters that contain 0.05 part of acetate, obtains sour molten shitosan; Prepare 5 parts in addition and contain 0.5 part of NaHCO
3Sodium bicarbonate solution.
1.5 parts of montmorillonites that obtain through the purification of sodium fluoride modified alta-mud are scattered in 30 parts of water, after 1500 rev/mins mixing speeds are disperseed 1 minute, add among 20 parts of oily ASA, stirring and emulsifying is 3 minutes under 6000 rev/mins rotating speed, obtains the stable ASA emulsion of montmorillonite; Afterwards again under 6000 rev/mins mixing speed, the sour molten shitosan that adds above-mentioned preparation, stir after 5 minutes, add the sodium bicarbonate solution of above-mentioned preparation, continue to stir 5 minutes, obtain milky O/W type ASA emulsion, emulsion pH value is about 7, and the mass percent of ASA is about 33%, about emulsion liquid-drop diameter 2～3 μ m, emulsion descended centrifugal 10 minutes at 3000 rev/mins through centrifuge, did not see layering.
Get 50 parts of Straw Pulp and 50 share softwood pulps and be dispersed in 9900 parts of water, after being uniformly dispersed, add 2 parts of above-mentioned ASA emulsion liquid, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 49s.
Embodiment 7
The shitosan of 0.03 part of deacetylation 85.9%, viscosity 750mPas is dissolved in 6 parts of deionized waters that contain 0.06 part of acetate, obtains sour molten shitosan; Prepare 14 parts of ammoniacal liquor that contain 0.6 part of ammonia in addition.With 1.4 parts of modified montmorillonite used being scattered in 20 parts of water of natrium citricum, disperseed 2 minutes through 1000 rev/mins mixing speeds, obtain montmorillonite suspension.In montmorillonite suspension, add the above-mentioned sour molten shitosan and the ammoniacal liquor of preparation in advance successively, continue to stir 10 minutes down, obtain the deposition modified montmorillonite suspension of shitosan at 1000 rev/mins.
The montmorillonite suspension that the shitosan of above-mentioned preparation is deposition modified adds among 20 parts of oily ASA, and stirring and emulsifying is 15 minutes under 2000 rev/mins rotating speed.Make milky O/W type ASA emulsion, emulsion pH value is about 7, and the mass percent of ASA is about 25%, emulsion liquid-drop diameter 1～2 μ m, and emulsion descended centrifugal 10 minutes at 4000 rev/mins through centrifuge, did not see variation.
Get 100 parts of hardwood pulps and be dispersed in 9900 parts of water, after being uniformly dispersed, add 2 parts of above-mentioned ASA emulsion liquid, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 67s.
Embodiment 8
The shitosan of 0.03 part of deacetylation 95%, viscosity 1000mPas is dissolved in 6 parts of deionized waters that contain 0.06 part of acetate, obtains sour molten shitosan; It is standby to prepare 2 parts of ammoniacal liquor that contain 0.06 part of ammonia in addition.
With 1.5 parts of modified montmorillonite used being scattered in 32 parts of water of natrium citricum, after 1000 rev/mins mixing speeds are disperseed 1 minute, add among the ASA of 20 parts of oilies, under 2000 rev/mins mixing speed, stirred 15 minutes, obtain the stable ASA emulsion of montmorillonite; Afterwards again under 2000 rev/mins mixing speed, the sour molten shitosan that adds above-mentioned preparation, stir after 5 minutes, add the ammoniacal liquor of above-mentioned preparation, continue to stir 15 minutes, obtain milky O/W type ASA emulsion, the mass percent of ASA is about 33%, and emulsion pH value is about 5.6, and the liquid-drop diameter of emulsion is about 1～3 μ m, emulsion centrifugal 10 minutes through 4000 rev/mins rotating speed is not seen variation.
Get 50 parts of hardwood pulps and 50 parts of straw pulps are dispersed in 9900 parts of water, after being uniformly dispersed, add 2 parts of above-mentioned ASA emulsions, 2 parts of Al
2(SO
4)
3, mix the back and form paper stock, and copy the about 60/m of formulation amount by quick kayser method sheet forming apparatus
2Handsheet, handsheet is with after the drying cylinder oven dry, utilizing liquid osmosis (GB/T5405-2002) to record the handsheet degree of sizing is 52s.
Claims (6)
1. the preparation method of the ASA papermaking sizing agent emulsion of a high stability is characterized in that adopting following steps:
Montmorillonite is dispersed in the water, makes montmorillonite suspension, and under mechanical agitation, ASA mixes with oily, prepare the stable ASA emulsion of montmorillonite; In above-mentioned emulsion, add the chitosan solution of diluted acid dissolving then earlier, add weak base again,, prepare stable O/W type ASA emulsion through mechanical agitation;
Or under mechanical agitation, the chitosan solution of montmorillonite, weak base and diluted acid dissolving is dispersed in the water jointly, prepare the deposition modified montmorillonite particulate emulsifying agent of shitosan; Under mechanical agitation, mentioned emulsifier is mixed with oily ASA then, prepare stable O/W type ASA emulsion;
Described ASA is 1: 1～4 with the mass ratio of the Total Water that constitutes ASA emulsion; The mass ratio of described montmorillonite and ASA is 1: 5～25;
The diluted acid of described dissolving shitosan is acetic acid or hydrochloric acid; The mass ratio of diluted acid and shitosan is 1: 0.1～1; The mass ratio of shitosan and ASA is 1: 100～2000; The deacetylation of shitosan is greater than 85%, and viscosity is less than 1000mPas.
Described weak base is ammoniacal liquor, sodium carbonate or sodium bicarbonate; The mass ratio of weak base and shitosan is 2: 1～20: 1.
2. preparation method according to claim 1, it is characterized in that: montmorillonite suspension mixes with ASA's, mixing of the ASA emulsion that the chitosan solution of diluted acid dissolving, weak base and montmorillonite are stable, mechanical agitation in montmorillonite particulate emulsifying agent that shitosan is deposition modified and the mixed process of ASA is 2000～12000 rev/mins of mixing speeds, mixing time 2～15 minutes; Mechanical agitation in preparation montmorillonite particulate emulsifying agent process is 500～2000 rev/mins of mixing speeds, mixing time 1～30 minute.
3. preparation method according to claim 1 is characterized in that: described montmorillonite is by natural sodium bentonite or through the acquisition of purifying of the calcium-base bentonite of sodium modification, the content of montmorillonite is greater than 90%.
4. preparation method according to claim 1 is characterized in that: described ASA is 1: 2～3 with the mass ratio of the Total Water that constitutes ASA emulsion, and the mass ratio of montmorillonite and ASA is 1: 10～20; The diluted acid of described dissolving shitosan is an acetic acid; The mass ratio of shitosan and ASA is 1: 200～800; The viscosity of shitosan is less than 750mPas; Described weak base is ammoniacal liquor, and the mass ratio of ammoniacal liquor and shitosan is 5～10: 1.
5. preparation method according to claim 2, it is characterized in that: montmorillonite suspension mixes with ASA's, mixing of the ASA emulsion that the chitosan solution of diluted acid dissolving, weak base and montmorillonite are stable, mechanical agitation in montmorillonite particulate emulsifying agent that shitosan is deposition modified and the mixed process of ASA is 5000～10000 rev/mins of mixing speeds, mixing time 3～10 minutes.
6. preparation method according to claim 1 is characterized in that: described montmorillonite is obtained by the neutral sodium Purification of Bentonite through sodium fluoride or natrium citricum modification.
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| CN102199899B (en) * | 2011-04-26 | 2012-09-26 | 山东轻工业学院 | Alkenyl succinic anhydride sizing agent |
| CN102268839B (en) * | 2011-07-25 | 2013-04-10 | 华南理工大学 | Method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent |
| CN103225234B (en) * | 2013-03-25 | 2015-06-03 | 华南理工大学 | Method for preparing magnetism papermaking sizing agent stabilized by magnetism solid particle emulsification |
| CN103194934B (en) * | 2013-03-29 | 2016-01-06 | 华南理工大学 | A kind of preparation method by the glue used in paper-making of chip solid particle emulsification |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997049865A1 (en) * | 1996-06-25 | 1997-12-31 | Buckman Laboratories International, Inc. | Asa sizing emulsions containing low and high molecular weight cationic polymers |
| CN1112477C (en) * | 1996-02-23 | 2003-06-25 | 希巴特殊化学水处理有限公司 | Sizing of paper |
| CN1242118C (en) * | 2000-05-30 | 2006-02-15 | 赫尔克里士公司 | Use of alkenyl succinic anhydride compsns., and its uses |
| CN101333789A (en) * | 2008-06-26 | 2008-12-31 | 山东轻工业学院 | Method for preparing ASA paper-making sizing agent emulsion |
| CN101397353A (en) * | 2008-11-17 | 2009-04-01 | 陕西科技大学 | Method for preparing high molecule emulsifying agent for ASA |
-
2009
- 2009-04-09 CN CN2009100204474A patent/CN101574834B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112477C (en) * | 1996-02-23 | 2003-06-25 | 希巴特殊化学水处理有限公司 | Sizing of paper |
| WO1997049865A1 (en) * | 1996-06-25 | 1997-12-31 | Buckman Laboratories International, Inc. | Asa sizing emulsions containing low and high molecular weight cationic polymers |
| CN1242118C (en) * | 2000-05-30 | 2006-02-15 | 赫尔克里士公司 | Use of alkenyl succinic anhydride compsns., and its uses |
| CN101333789A (en) * | 2008-06-26 | 2008-12-31 | 山东轻工业学院 | Method for preparing ASA paper-making sizing agent emulsion |
| CN101397353A (en) * | 2008-11-17 | 2009-04-01 | 陕西科技大学 | Method for preparing high molecule emulsifying agent for ASA |
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