CN102268839B - Method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent - Google Patents
Method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent Download PDFInfo
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Abstract
The invention provides a method for preparing Pickering emulsion type alkenyl succinic anhydrides (ASA) papermaking sizing agent. The method comprises the following steps of: intercalating quaternary ammonium salt into nano cation-based modified montmorillonite to prepare nano solid fine grain emulsifier; dispersing the nano solid fine grain emulsifier and magnesium salt into deionized water to form a water phase, mixing the water phase and oil phase ASA, and emulsifying the mixture through high speed shearing to obtain the Pickering emulsion type ASA papermaking sizing agent, wherein the volume ratio of the oil phase to the water phase is (1:1)-(1:6). The Pickering emulsion type ASA papermaking sizing agent is coupled with the emulsion and stabilization characteristics of organic surface active substances and inorganic solid fine grains; compared with the emulsion which is emulsified and stabilized by independently using the surface active substances, the Pickering emulsion type ASA papermaking sizing agent is more stable and higher in sizing efficiency; furthermore, the preparation process is simple, and the ASA can be emulsified into stable emulsion without adding any surfactant and high-molecule polyelectrolyte; and the using amount of the emulsifier is small and the emulsifying cost is low.
Description
Technical field
The present invention relates to the preparation method of glue used in paper-making, particularly the preparation method of Pickering emulsion-type ASA glue used in paper-making.
Background technology
The twentieth century paper industry is copied the paper system by acidity and is turned to neutral and alkali to copy paper, 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.According to statistics, 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 take alkyl ketene dimer (AKD) and alkenyl succinic anhydride (ASA) as main, big-and-middle-sized paper plant gradually adopts ASA at present.Especially in recent years, owing to ASA sizing agent reactivity is high, the sizing material cost is low, curing speed is widely used in fine paper and cardboard internal sizing soon, particularly be applicable to the applying glue of the large high-speed paper machine of on-line coater.Yet, 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, therefore hydrolysate can cause the paper making obstacle and reduce sizing efficiency, requires it can be by quick emulsification when using ASA, and the emulsion after the emulsification should be used as early as possible.And alkenyl succinic anhydride (ASA) not only very easily is hydrolyzed, and alcoholysis, ammonia solution also very easily occur, so alcohols, carboxylic acids, ammoniac compounds should not be as the emulsifying agent of ASA.The at present emulsification of ASA sizing agent 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, so that the ASA emulsifying process is rather complicated, wayward, and usually causes the problems such as deposition, obstruction woollen blanket.Surfactant wherein also brings certain adverse effect to applying glue, and environment is also brought certain pollution.
The Pickering emulsion is called again solid (particle) stable type 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 at present emulsification of ASA sizing agent 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 sizing efficiency also has sterilization.Although these inventions have been exempted starch gelatinization to 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 a small amount 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 Pickering emulsion-type ASA glue used in paper-making, that nano modification cation radical montmorillonite and quaternary ammonium salt is composite, make nano-solid particulate emulsifying agent, and with it as ASA emulsification and stabilizing agent, nano-solid particulate emulsifying agent and magnesium salts be scattered in make nano-solid particulate emulsifying agent suspension in the deionized water, under the high speed shear condition, carry out emulsification with ASA again, thereby make Pickering emulsion-type ASA glue used in paper-making.
Purpose of the present invention specifically is achieved through the following technical solutions:
(1) preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: the nano modification na-montmorillonite is scattered in the deionized water, then take by weighing with the montmorillonite mass ratio is the quaternary ammonium salt of 1:3 ~ 1:8, join in the described suspension, stir 0.5h～2h at 50 ℃～90 ℃ lower constant temperature, leave standstill cool to room temperature, then carry out extracting, the resulting decorating film water of extracting cyclic washing detects without Br to scrub raffinate
-, Cl
-Till the ion, cross 200 mesh sieves after then the decorating film oven dry being ground, the gained residue on sieve is nano-solid particulate emulsifying agent;
(2) preparation of Pickering emulsion-type ASA sizing agent: nano-solid particulate emulsifying agent is mixed with magnesium salts and disperse in the deionized water, stir 1 min～5 min, make solia particle emulsifying agent suspension; The ASA sizing agent is mixed the rear shear agitation of carrying out with solia particle emulsifying agent suspension by the volume ratio of 1:1～1:6 under room temperature, shear rate is 3000r/min～12000r/min, mixing time is 1min～15min, makes Pickering emulsion-type ASA sizing agent emulsion; Wherein the quality of nano-solid particulate emulsifying agent is 4%～10% of ASA sizing agent quality; The magnesium salts consumption is 0.01mol/L～1mol/L in the described solia particle emulsifying agent suspension.
Described quaternary ammonium salt is 12～octadecyl trimethyl quaternary ammonium salt; Described magnesium salts is magnesium chloride, magnesium nitrate, magnesium sulfate or magnesium phosphate.
Described 12～octadecyl trimethyl quaternary ammonium salt is 12～Cetyltrimethylammonium bromide or 12～octadecyl trimethyl ammonium chloride.
Above-mentioned nano modification cation radical montmorillonite as the main body emulsifying agent of preparation Pickering emulsion-type ASA, is the key emulsion stabilizer of Pickering emulsion in the present invention.Its cation radical is sodium ion, calcium ion, magnesium ion, lithium ion or ammonium ion.Be preferably sodium ion.
The nanometer na-montmorillonite can be natural na-montmorillonite, also can be the na-montmorillonite through the whole bag of tricks and sodium agent modification, but preferably through the neutral nanometer sodium montmorillonite of sodium fluoride modification or natrium citricum modification.
The content of montmorillonite is greater than 90% in the described nano modification cation radical montmorillonite.
As preferably, the volume ratio of ASA sizing agent and solia particle emulsifying agent suspension is 1:2～1:3.
ASA sizing agent among the present invention is average carbon number C
14～C
20Enetutanedioic acid anhydride., exist with liquid form at normal temperatures, be the various ASA industrial products for paper-making sizing without emulsification.
The middle ASA of step (2) mixes with solia particle emulsifying agent suspension, both under stirring action, the ASA of oily was added in the solia particle suspension, also solia particle suspension is under agitation joined among the ASA of oily, join in the solia particle suspension but more preferred scheme is ASA with oily.
The present invention can be provided by any stirring or mechanical shearing equipment at ASA and the mixed shear agitation of solia particle suspension, require mixing speed greater than 3000r/min, as preferably, be cut into 5000r/min～12000r/min, mixing time is 2min～10 min, it is less to obtain particle diameter, the ASA emulsion that emulsion is more stable.
Compared with prior art, the present invention has the following advantages:
(1) preparation method's emulsifying process of ASA emulsion of the present invention simply, does not need to add any conventional surfactant and complex polyelectrolyte particle just can be emulsified into ASA stable emulsion;
(2) the present invention's the two emulsification advantage of conventional emulsion and Pickering emulsion that has been coupled, the emulsion that surface reactive material and the stability of emulsion of the common emulsification of inoganic solids particulate are more stable than independent use surfactant stable much higher, therefore can prepare the ASA emulsion of high stability, high sizability, but and the amount of surfactant of adding in the decrease ASA emulsion process and thus to the adverse effect of ASA applying glue, improve concentration and the stability of ASA emulsion, reduce cost, improve environmental pollution.
Description of drawings
Fig. 1 is the optical microscope image after the drop of Pickering emulsion-type ASA sizing agent that embodiment 1 is prepared amplifies 1000 times.
The specific embodiment
Embodiment 1
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: with nanoscale sodium chloride modified na-montmorillonite (original soil is taken from Linan, Zhejiang) and hexadecyltrimethylammonium chloride (CTAC) in mass ratio the 4:1 ratio mix and be scattered in the water, at 65 ℃ of lower constant temperature stirring reaction 1h, obtain suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, and decorating film ground 200 mesh sieves after 80 ℃ of lower oven dry, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of industrial goods octadecylene base succinyl oxide (ODSA, available from Kemira kemira chemical company), nano-solid particulate emulsifying agent and the magnesium chloride of above-mentioned preparation are scattered in the deionized water, stir 5min and make solia particle emulsifying agent suspension, the magnesium chloride consumption is 0.03mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2, with FLUKO emulsification pretreatment machine (Shanghai Frock Fluid Machinery Manufacture Co., Ltd., together lower) emulsification 3min under 5000 r/min rotating speeds, nano-solid particulate emulsifier is that 5%(is to the ASA mass percent, together lower), the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes; Its viscosity is 0.185Pas, particle mean size 4 ~ 6 μ m, and 10min is unchanged for prepared pickering emulsion-type ASA sizing agent centrifugal under centrifuge (rotating speed 3000r/min), separates out without the phase body, without demulsifying phenomenon, places 6h without significant change.Get the ASA sizing agent drop that makes and place the optical microphotograph Microscopic observation, Fig. 1 is its droplet distribution and form thereof after amplifying 1000 times under the light microscope, can find out that pickering emulsion-type ASA sizing agent droplet distribution is even, particle diameter is less, and what be attached to nano-solid particle success on the oil-water interfaces has played emulsification and stabilization.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the square handshcet former of PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 100% hardwood pulp, and ASA consumption 0.5%(is to oven dry stock, and is lower same), CPAM consumption 0.03%(is to oven dry stock, and is lower same), Al
2(SO
4)
3Consumption 1%(is to oven dry stock, and is lower same).The sizing degree is 66s(GB/T5405-2002, and is lower same).
Embodiment 2
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nanoscale sodium fluoride modified montmorillonite used (original soil is taken from Shandong Zibo), hexadecyltrimethylammonium chloride (CTAC) are scattered in the deionized water in the ratio mixing of 4:1, add thermal agitation 1h 60 ℃ of lower waters bath with thermostatic control, obtain suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is ground 200 mesh sieves after 105 ℃ of lower oven dry, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (ODSA, take from Shandong Morning Ring Paper Indusrty Co., Ltd), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium chloride are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium chloride consumption is 0.01mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2, with FLUKO emulsification pretreatment machine emulsification 5min under 8000 r/min rotating speeds, nano-solid particulate emulsifier is 8%, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, and its viscosity is 0.141Pas, particle mean size 3～5 μ m, place 6h without significant change, under 4000r/min, separated out without water in centrifugal 30 minutes, show to have good stability.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 100% hardwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 1%, sizing degree are 74s.
Embodiment 3
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nanoscale sodium base modified montmorillonite used (original soil is taken from Liaoning), hexadecyltrimethylammonium chloride (CTAC) are scattered in the deionized water in the ratio mixing of 4.2:1, add thermal agitation 2h 80 ℃ of lower waters bath with thermostatic control, obtain suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is ground 200 mesh sieves after 105 ℃ of lower oven dry, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (ASA, available from Kemira kemira chemical company), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium sulfate are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium sulfate consumption is 0.05mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2, with FLUKO emulsification pretreatment machine emulsification 2min under 10000 r/min rotating speeds, nano-solid particulate emulsifier is 10%, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, its viscosity is 0.112Pas, particle mean size is 2～5 μ m, place 6h without significant change, place centrifuge with the 4000r/min rotating speed after centrifugal 20 minutes without lamination.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the square handshcet former of PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is the mixing slurry of 30% hardwood pulp and 70% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 71s.
Embodiment 4
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nanometer natrium citricum modified na-montmorillonite (original soil is taken from Zhejiang), softex kw (CTAB) are scattered in the deionized water in the ratio mixing of 4.2:1, add thermal agitation 2h 80 ℃ of lower waters bath with thermostatic control, obtain suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the bromide ion to scrub raffinate, then decorating film is ground 200 mesh sieves after 105 ℃ of lower oven dry, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base succinyl oxide (ODSA, take from Shandong Morning Ring Paper Indusrty Co., Ltd), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium sulfate are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium sulfate consumption is 0.05mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:3, be 15% with FLUKO emulsification pretreatment machine emulsification 3min nano-solid particulate emulsifier under 10000 r/min rotating speeds, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, its viscosity 0.123Pas, particle mean size 2～4 μ m, emulsion is placed 6h without significant change.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 77s.
Embodiment 5
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nanometer sodium base modified montmorillonite used (original soil is taken from Shandong Zibo), hexadecyltrimethylammonium chloride (CTAC) are scattered in the deionized water in the ratio mixing of 4.5:1, add thermal agitation 1h 60 ℃ of lower waters bath with thermostatic control, to suspension, the described suspension of extracting, the resulting decorating film water of extracting cyclic washing, to scrub raffinate, detect without till the chlorion, then decorating film was ground 200 mesh sieves after 105 ℃ of lower oven dry, residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (ASA, available from Shanghai Kemira kemira chemical company), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium chloride are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium chloride consumption is 0.1mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2, with FLUKO emulsification pretreatment machine emulsification 5min under 8000 r/min rotating speeds, nano-solid particulate emulsifier is 18%, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, its viscosity is 0.248Pas, particle mean size 2～4 μ m, place 6h without significant change, centrifugal 30 minutes without lamination.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 75s.
Embodiment 6
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nanometer sodium base modified montmorillonite used (original soil is taken from Weifang, Shandong), hexadecyltrimethylammonium chloride (CTAC) are scattered in the deionized water by the mass ratio mixing of 5:1, add thermal agitation 1h 80 ℃ of lower waters bath with thermostatic control, to suspension, the described suspension of extracting, the resulting decorating film water of extracting cyclic washing, to scrub raffinate, detect without till the chlorion, then decorating film was ground 200 mesh sieves after 105 ℃ of lower oven dry, residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (ODSA, available from Shanghai Kemira kemira chemical company), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium nitrate are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium nitrate consumption is 0.05mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:3, with FLUKO emulsification pretreatment machine emulsification 3min under 10000 r/min rotating speeds, nano-solid particulate emulsifier is 20%, the homogeneous breast pickering emulsion-type ASA sizing agent that makes, its viscosity is 0.336Pas, and particle mean size 4～7 μ m place 6h without significant change.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, page is dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 2%.The sizing degree is 124s.
Embodiment 7
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: the mass ratio mixing of nano modification na-montmorillonite (original soil is taken from Weifang, Shandong) and hexadecyltrimethylammonium chloride 5:1 is scattered in the deionized water, stirring reaction 1h under 65 ℃ of waters bath with thermostatic control obtains suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is ground 200 mesh sieves again 105 ℃ of lower oven dry, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (ODSA, available from Shanghai Kemira kemira chemical company), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium nitrate are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium nitrate consumption is 0.02mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2, with FLUKO emulsification pretreatment machine emulsification 2min under 11000 r/min rotating speeds, nano-solid particulate emulsifier is 5%, the homogeneous breast pickering emulsion-type ASA sizing agent that makes, and its viscosity is 0.121Pas, particle mean size is 0.5～2 μ m, place 12h without significant change,, show to have good stability without significant change through centrifugal 30 minutes of 4000r/min.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, the scraps of paper are dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, sodium-ionized bentonite consumption 0.2%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 83s.
Embodiment 8
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nano modification na-montmorillonite (original soil is got Linan, Zhejiang) and hexadecyltrimethylammonium chloride are mixed according to the mass ratio of 5.5:1 and be scattered in the deionized water, stirring reaction 1h under 65 ℃ of waters bath with thermostatic control obtains suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is dried and ground 200 mesh sieves under 105 ℃, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (ODSA, available from the Shandong Morning Ring Paper Indusrty), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium chloride are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium chloride consumption is 0.5mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2, be 5% with FLUKO emulsification pretreatment machine emulsification 4min nano-solid particulate emulsifier under 8000 r/min rotating speeds, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, its viscosity is 0.549Pas, and particle mean size 3～7 μ m place 6h without significant change, centrifugal 30 minutes without significant change, good stability.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, the scraps of paper are dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, sodium-ionized bentonite consumption 0.2%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 65s, with the contact angle of water be 120 °, sizability is good.
Embodiment 9
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: sodium fluoride modification sodium-ionized bentonite (original soil is taken from Liaoning) and the mass ratio of hexadecyltrimethylammonium chloride according to 6:1 are scattered in the deionized water, stirring reaction 1h under 80 ℃ of waters bath with thermostatic control obtains suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is dried and ground 200 mesh sieves under 105 ℃, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing a certain amount of technical grade octadecylene base butanedioic acid (Shandong Morning Ring Paper Indusrty), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium phosphate are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium phosphate consumption is 1mol/L in the solia particle emulsifying agent suspension; Add ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:2 again, with FLUKO emulsification pretreatment machine emulsification 3min under 10000 r/min rotating speeds.The homogeneous oyster white pickering emulsion-type ASA sizing agent that makes; Nano-solid particulate emulsifier is 10%, and its viscosity is 0.452Pas, and particle mean size is 1～3 μ m, places 48h without significant change, and stability better without significant change in centrifugal 20 minutes.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, the scraps of paper are dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, sodium-ionized bentonite consumption 0.2%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 70s, with the contact angle of water be 123.8 °, sizability is better.
Embodiment 10
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nanoscale sodium fluoride modification sodium-ionized bentonite (original soil is taken from Liaoning) and the mass ratio of hexadecyltrimethylammonium chloride according to 6.5:1 are scattered in the deionized water, stirring reaction 1h under 70 ℃ of waters bath with thermostatic control obtains suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is dried grinding and is crossed 200 mesh sieves under 105 ℃, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing industrial glue used in paper-making ASA(and take from Shandong Morning Ring Paper Indusrty Co., Ltd), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium chloride are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium chloride consumption is 0.5mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:3, with FLUKO emulsification pretreatment machine emulsification 3min under 10000 r/min rotating speeds, nano-solid particulate emulsifier is 8%, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, its viscosity is 0.065Pas, particle mean size 2～7 μ m place 48h without significant change, with the centrifugation 30 minutes under the 4000r/min centrifugal speed of prepared sizing agent, without significant change, illustrate that stability better.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, the scraps of paper of copying are dried in FI119 type electrothermal drying cylinder, Substance 60g/m
2, slurry is 50% hardwood pulp, 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 1%.The sizing degree is 77s, with the contact angle of water be 113.3 °, sizing efficiency is good.
Embodiment 11
The preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: nano level modified sodium-ionized bentonite (original soil is taken from Liaoning) and the hexadecyltrimethylammonium chloride mass ratio according to 8:1 is scattered in the deionized water, stirring reaction 2h under 75 ℃ of waters bath with thermostatic control obtains suspension; The described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without till the chlorion to scrub raffinate, then decorating film is ground 200 mesh sieves 105 ℃ of lower oven dry, and residue on sieve is nano-solid particulate emulsifying agent;
The preparation of Pickering emulsion-type ASA sizing agent: take by weighing industrial glue used in paper-making ASA(ODSA, available from Shandong Morning Ring Paper Indusrty Co., Ltd), the nano-solid particulate emulsifying agent of above-mentioned preparation and magnesium nitrate are scattered in deionized water for stirring 5min make solia particle emulsifying agent suspension, the magnesium nitrate consumption is 1mol/L in the solia particle emulsifying agent suspension; Add again ASA, keeping the volume ratio of ASA and solia particle emulsifying agent suspension is 1:1, with FLUKO emulsification pretreatment machine, under 12000 r/min rotating speeds emulsification 5min, nano-solid particulate emulsifier is 10%, the homogeneous oyster white pickering emulsion-type ASA sizing agent that makes, its viscosity is 0.985Pas, particle mean size is 2.5～6 μ m, place 48h without significant change, not stratified behind the centrifugal 30min.
Prepared pickering emulsion-type ASA sizing agent is carried out plasm-glue-blending, the plasm-glue-blending effect: copy paper at the circular handshcet former of PTI, the scraps of paper are dried in FI119 type electrothermal drying cylinder, quantitatively 60g/m
2Slurry is 50% hardwood pulp and 50% softwood pulp, ASA consumption 0.5%, CPAM consumption 0.03%, Al
2(SO
4)
3Consumption 0.5%.The sizing degree is 84s, with the contact angle of water be 121 °.
Claims (8)
1. the preparation method of solid particle stable type emulsion-type ASA glue used in paper-making is characterized in that step is as follows:
(1) preparation of the nano-solid particulate emulsifying agent of inorganic-organic complex: the nano modification na-montmorillonite is mixed with the mass ratio of quaternary ammonium salt by 3: 1～8: 1, and be scattered in the water, stir 0.5h～2h at 50 ℃～90 ℃ lower constant temperature, leave standstill cool to room temperature, obtain suspension; Then the described suspension of extracting, the resulting decorating film water of extracting cyclic washing detects without Br to scrub raffinate
-, Cl
-Till the ion, cross 200 mesh sieves after the decorating film oven dry being ground, the gained residue on sieve is nano-solid particulate emulsifying agent again;
(2) preparation of solid particle stable type emulsion-type ASA sizing agent: nano-solid particulate emulsifying agent is mixed with magnesium salts and disperse in the deionized water, stir 1min～5min, make solia particle emulsifying agent suspension; The ASA sizing agent is mixed the rear shear agitation of carrying out with solia particle emulsifying agent suspension by 1: 1～1: 6 volume ratio under room temperature, shear rate is 3000r/min～12000r/min, mixing time is 1min～15min, makes solid particle stable type emulsion-type ASA sizing agent; Wherein the quality of nano-solid particulate emulsifying agent is 4%～10% of ASA sizing agent quality; The magnesium salts consumption is 0.01mol/L～1mol/L in the described solia particle emulsifying agent suspension.
2. preparation method according to claim 1 is characterized in that described ASA sizing agent mixes by 1: 2～1: 3 volume ratio with solia particle emulsifying agent suspension.
3. preparation method according to claim 1 is characterized in that described quaternary ammonium salt is 12～octadecyl trimethyl quaternary ammonium salt, and described magnesium salts is magnesium chloride, magnesium nitrate, magnesium sulfate or magnesium phosphate.
4. preparation method according to claim 3 is characterized in that described 12～octadecyl trimethyl quaternary ammonium salt is 12～Cetyltrimethylammonium bromide or 12～octadecyl trimethyl ammonium chloride.
5. preparation method according to claim 2 is characterized in that the content of montmorillonite in the described nano modification na-montmorillonite is greater than 90%.
6. preparation method according to claim 5 is characterized in that described nano modification na-montmorillonite is the neutral nanometer sodium montmorillonite through sodium fluoride modification or natrium citricum modification.
7. preparation method according to claim 1 is characterized in that described shear rate is 5000r/min～12000r/min, and mixing time is 2min～10min.
8. preparation method according to claim 1 is characterized in that described ASA sizing agent is average carbon number C
14～C
20Enetutanedioic acid anhydride.
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| 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 |
| CN103233392B (en) * | 2013-03-29 | 2015-07-01 | 华南理工大学 | Preparation method of solid particle emulsified and stabilized papermaking sizing agent |
| CN103451994B (en) * | 2013-09-02 | 2016-05-25 | 齐鲁工业大学 | The method of quaternary ammonium salt-modified hectorite emulsifying agent and emulsification ASA thereof a kind of |
| CN103451995B (en) * | 2013-09-02 | 2015-09-30 | 齐鲁工业大学 | ASA sizing emulsions that a kind of quaternary ammonium salt-modified hectorite is stable and preparation method thereof |
| CN103613700B (en) * | 2013-11-13 | 2016-04-06 | 陕西科技大学 | A kind of Pickering emulsion polymerization prepares the method for polyacrylic ester/Nano-ZnO Hybrid Coatings printing adhesive |
| CN104801213B (en) * | 2015-03-07 | 2018-05-29 | 中石化石油工程技术服务有限公司 | A kind of Pickering emulsion preparation methods of high viscous high stable |
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| CN108951280B (en) * | 2018-06-29 | 2020-09-22 | 华南理工大学 | Preparation method and application of fluorescent ASA Pickering emulsion |
| CN110004766B (en) * | 2019-04-29 | 2021-05-18 | 齐鲁工业大学 | Preparation method of alginate-coated calcium carbonate particle stable papermaking sizing agent emulsion |
| CN112661384B (en) * | 2020-12-03 | 2022-12-30 | 深圳市科拉达精细化工有限公司 | Method for reconstructing high-water-content oil sludge |
| CN112551838B (en) * | 2020-12-03 | 2022-12-30 | 深圳市科拉达精细化工有限公司 | Treatment method of high-water-content oil sludge |
| CN114059386A (en) * | 2021-11-16 | 2022-02-18 | 中国科学院理化技术研究所 | Water-based paint with waterproof and oil-proof performance and preparation method and application 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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| RU2429323C2 (en) * | 2005-12-21 | 2011-09-20 | Акцо Нобель Н.В. | Paper sizing |
| CN101333789B (en) * | 2008-06-26 | 2011-07-20 | 山东轻工业学院 | Method for preparing ASA paper-making sizing agent emulsion |
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