CN102635021B - Preparation method of high-reactivity cation AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent - Google Patents
Preparation method of high-reactivity cation AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-reactivity cation AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent, which comprises the following steps of: firstly, obtaining a reactive emulsifier by using OP-10, maleic anhydride and dodecanol as raw materials; carrying out free radical copolymerization on the reactive emulsifier, phenylethylene, methyl acrylate and acrylamine by using ammonium persulfate and sodium hydrogensulfite as initiators and using dodecanethiol as a molecular weight regulator; and finally, acidizing by using acetic acid to obtain a polymer which is an AKD emulsifier as well as an AKD emulsion stabilizer and a sizing synergist, and emulsifying the AKD by using the polymer as an emulsifying agent. The prepared neutral/alkaline sizing agent emulsion particle carries positive charges under the acidic condition, has stronger emulsification and dispersion capacities, is remarkably improved in sizing degree, and is better in retaining property and sizing effect.
Description
Technical field
The invention belongs to polymer chemistry sizing agent field, the preparation method of particularly in a kind of high reaction activity cation AKD/alkaline sizing agent.
Background technology
The major progress of modern applying glue technology be in/popularization of alkaline bleach liquor sizing technology, during acid papermaking is converted into/alkaline paper-making is the great change in world's papermaking history.In/alkaline bleach liquor sizing is in papermaking process, pH value is adjusted to more than 7, in principle without a kind of glue applying method of aluminum sulfate.In conventional/alkaline sizing agent alkyl ketene dimer (being called for short AKD) is the product of phase late 1940s research and development, AKD be a kind of can with the response type of fibrin reaction in/alkaline sizing agent, it can be as internal sizing agent, again can be as Cypres.Its design feature is to consist of active group and hydrophobic grouping, the fusing point of AKD is lower, active group quaternary lactonic ring energy under the hot conditions of Dryer Section of Paper Machine in molecule and the hydroxyl reaction on cellulose form beta-keto ester bond and are positioned on fiber, and hydrophobic group chain alkyl produces water resistant effect at fiber surface.By in AKD/alkaline bleach liquor sizing, the one way retention of Paper White Degree, feel, WATER RESISTANCE, physical strength, printability, resistance to ag(e)ing and filler etc. is all significantly improved.And can to adopt cheap powdered whiting be filler, reduced the content of harmful substance in plain boiled water, improved the cyclic utilization rate of plain boiled water, AKD is lower than the cost of acid accumulator size simultaneously.Adopt AKD carry out in/alkaline bleach liquor sizing can improve paper product quality and price, reduction energy consumption, improve environmental pollution and paper machine operation performance etc., therefore can obtain obvious economic benefit and social benefit, increasing papermaking enterprise is recognized superiority and the necessity of use in AKD/alkaline sizing agent.China's paper making raw material be take straw pulp as main, timber resource shortage, and secondary stock consumption increases, in utilization/alkaline bleach liquor sizing technology has realistic meaning.Follow in AKD/alkaline bleach liquor sizing technology progressively expands in China's Application Areas, technology is increasingly mature, in/benefit of alkaline paper-making progressively embodied, accelerated paper industry by acid papermaking in/trend that alkaline paper-making changes, in recent years AKD become domestic paper plant use at most, the most ripe, the most effectively in/alkaline sizing agent.
In AKD/alkaline bleach liquor sizing gives paper some excellent properties, also has its weak point simultaneously.AKD is unstable in water, AKD emulsion preparation and deposit in process easily hydrolysis and lost efficacy.During wet paper page drying position, the time that AKD at high temperature contact with water is longer, and AKD reacts with fiber and AKD vies each other with the hydrolysis that water carries out, and part AKD, because of hydrolysis inefficacy, causes degree of sizing decline or hysteresis.Improve in recent years and to improve the research of AKD emulsion property increasingly active, reduce the hydrolysis of AKD, improve the extent of reaction of AKD and fiber, development and production good emulsion stability and with the active high AKD emulsion of fiber-reactive be that China's papermaking researcher is made great efforts the problem of studying always.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the preparation method of the object of the present invention is to provide in a kind of high reaction activity cation AKD/alkaline sizing agent, in gained/alkaline sizing agent hydrolysis, there is good storage stability, even if there is water to exist under hot environment, also there is high reactivity, thereby greatly improved reaction efficiency and the sizing efficiency of sizing material.
For achieving the above object, the technical solution used in the present invention is:
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, comprise following concrete steps:
The first step, OP-10 and maleic anhydride are added in the first reactor and to react 1.0-1.5 hour 75-80 ℃ time, then add lauryl alcohol in 90-95 ℃ of reaction 2.0-2.5 hour, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by reactive emulsifier, styrene, methyl acrylate, diallylamine and lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by ammonium persulfate, sodium hydrogensulfite and deionized water with mass ratio at 2: 1: 30,
The 4th step adds deionized water in the second reactor, is warming up to 55-65 ℃, adds respectively initiator solution and mixed solution, and the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.0-1.5 hour,
The 5th step, reinforced after in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value, to 4-5, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add AKD emulsifying agent and AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 70-80 ℃, after AKD melting, stir 40-50 minute, then under agitation add the deionized water of 70-80 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 20-30MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value, to 4-5, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 70-90 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 7.5-8.5, in high reaction activity cation AKD/alkaline sizing agent consumption 4.0-6.5Kg/t paper, after lower machine, the Cobb value of wood-free paper is 23-28g/m
2, and save sizing material 27-32%.
The present invention does not adopt low molecule emulsifying agent in preparation process, and reactive emulsifier becomes a part for strand in polymerization process with covalent bonds, thereby has eliminated the weak point that low molecule emulsifying agent brings.The polymer obtaining is the emulsifying agent of AKD, again stabilizing agent and the sizing synergist of AKD emulsion, using it as emulsifying agent, be applied to the emulsification of AKD, in preparation/alkaline sizing agent emulsion particle is positively charged under acid condition, there is stronger emulsification and dispersibility, can AKD be carried out effective emulsification and fully be disperseed, obtain having the sizing agent emulsion of good stability.In paper-making process, (in/alkali condition) stabilizing agent lost efficacy, and was conducive to AKD and the cellulose generation degree of sizing that reacts, and this is the improvement greatly to starch series AKD emulsion emulsifying technology.
The specific embodiment
Below will with specific embodiment, the present invention is described in further detail.
Embodiment mono-
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.5 hours 75 ℃ time, then add 10 grams of lauryl alcohols in 90 ℃ of reactions 2.5 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 55 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.5 hours
The 5th step, reinforced after in 80 ℃ of insulation reaction 3.0 hours,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value to 4, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 70 ℃, after AKD melting, stir 50 minutes, then under agitation add the deionized water of 70 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 20MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 70 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 7.5, in high reaction activity cation AKD/alkaline sizing agent consumption 4.0Kg/t paper, after lower machine, the Cobb value of wood-free paper is 28g/m
2, and save sizing material 32%.
Embodiment bis-
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.4 hours 76 ℃ time, then add 10 grams of lauryl alcohols in 91 ℃ of reactions 2.4 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 57 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.4 hours
The 5th step, reinforced after in 82 ℃ of insulation reaction 2.8 hours,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value to 4.2, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 72 ℃, after AKD melting, stir 48 minutes, then under agitation add the deionized water of 72 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 22MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.2, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 74 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 7.7, in high reaction activity cation AKD/alkaline sizing agent consumption 4.5Kg/t paper, after lower machine, the Cobb value of wood-free paper is 27g/m
2, and save sizing material 31%.
Embodiment tri-
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.3 hours 77 ℃ time, then add 10 grams of lauryl alcohols in 92 ℃ of reactions 2.3 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 59 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.3 hours
The 5th step, reinforced after in 84 ℃ of insulation reaction 2.6 hours,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value to 4.4, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 74 ℃, after AKD melting, stir 46 minutes, then under agitation add the deionized water of 74 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 24MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.4, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 78 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 7.9, in high reaction activity cation AKD/alkaline sizing agent consumption 5.0Kg/t paper, after lower machine, the Cobb value of wood-free paper is 26g/m
2, and save sizing material 30%.
Embodiment tetra-
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.2 hours 78 ℃ time, then add 10 grams of lauryl alcohols in 93 ℃ of reactions 2.2 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 61 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.2 hours
The 5th step, reinforced after in 86 ℃ of insulation reaction 2.4 hours,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value to 4.6, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 76 ℃, after AKD melting, stir 44 minutes, then under agitation add the deionized water of 76 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 26MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.6, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 82 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 8.1, in high reaction activity cation AKD/alkaline sizing agent consumption 5.5Kg/t paper, after lower machine, the Cobb value of wood-free paper is 25g/m
2, and save sizing material 29%.
Embodiment five
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.1 hours 79 ℃ time, then add 10 grams of lauryl alcohols in 94 ℃ of reactions 2.1 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 63 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.1 hours
The 5th step, reinforced after in 88 ℃ of insulation reaction 2.2 hours,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value to 4.8, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 78 ℃, after AKD melting, stir 42 minutes, then under agitation add the deionized water of 78 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 28MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.8, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 86 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 8.3, in high reaction activity cation AKD/alkaline sizing agent consumption 6.0Kg/t paper, after lower machine, the Cobb value of wood-free paper is 24g/m
2, and save sizing material 28%.
Embodiment six
In high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.0 hours 80 ℃ time, then add 10 grams of lauryl alcohols in 95 ℃ of reactions 2.0 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 65 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.0 hours
The 5th step, reinforced after in 90 ℃ of insulation reaction 2.0 hours,
The 6th step, is down to greenhouse, and with vinegar acid for adjusting pH value to 5, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 80 ℃, after AKD melting, stir 40 minutes, then under agitation add the deionized water of 80 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 30MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 5, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD obtaining with the present invention/the emulsion extension of validity of alkaline sizing agent 90 days, use it for 70g/m
2in the plasm-glue-blending of wood-free paper, pH value is 8.5, in high reaction activity cation AKD/alkaline sizing agent consumption 6.5Kg/t paper, after lower machine, the Cobb value of wood-free paper is 23g/m
2, and save sizing material 27%.
In sum, the present invention adopts reactive emulsifier and styrene-acrylate to carry out copolyreaction, obtain cationic amine based polymer and replace cationic starch as the emulsion stabilizer of AKD, its positive electricity density is easy to adjust, the positive electricity adaptability of AKD micelle cohesion is strengthened, form the AKD sizing agent that is applicable to special wet end environment.Amine polymer has reduced hydrolysis tendency effectively to the adjustment of AKD emulsion particle electric charge, and makes the extension of validity of AKD emulsion.This emulsion has increased the affinity of AKD molecule and cellulose hydroxyl, improvement keeping on fiber, AKD particulate even also can be combined with fibre compact in the situation that paper moisture content increases, so degree of sizing obviously improves, and has good retention and sizing efficiency.
Claims (7)
1. a preparation method in high reaction activity cation AKD/alkaline sizing agent, is characterized in that, comprises following concrete steps:
The first step, OP-10 and maleic anhydride are added in the first reactor and to react 1.0-1.5 hour 75-80 ℃ time, then add lauryl alcohol in 90-95 ℃ of reaction 2.0-2.5 hour, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by reactive emulsifier, styrene, methyl acrylate, diallylamine and lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by ammonium persulfate, sodium hydrogensulfite and deionized water with mass ratio at 2: 1: 30,
The 4th step adds deionized water in the second reactor, is warming up to 55-65 ℃, adds respectively initiator solution and mixed solution, and the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.0-1.5 hour,
The 5th step, reinforced after in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value, to 4-5, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add AKD emulsifying agent and AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 70-80 ℃, after AKD melting, stir 40-50 minute, then under agitation add the deionized water of 70-80 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 20-30MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value, to 4-5, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
2. the preparation method of in a kind of high reaction activity cation AKD according to claim 1/alkaline sizing agent, is characterized in that, specifically comprises the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.5 hours 75 ℃ time, then add 10 grams of lauryl alcohols in 90 ℃ of reactions 2.5 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 55 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.5 hours
The 5th step, reinforced after in 80 ℃ of insulation reaction 3.0 hours,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value to 4, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 70 ℃, after AKD melting, stir 50 minutes, then under agitation add the deionized water of 70 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 20MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
3. the preparation method of in a kind of high reaction activity cation AKD according to claim 1/alkaline sizing agent, is characterized in that, specifically comprises the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.4 hours 76 ℃ time, then add 10 grams of lauryl alcohols in 91 ℃ of reactions 2.4 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 57 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.4 hours
The 5th step, reinforced after in 82 ℃ of insulation reaction 2.8 hours,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value to 4.2, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 72 ℃, after AKD melting, stir 48 minutes, then under agitation add the deionized water of 72 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 22MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.2, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
4. the preparation method of in a kind of high reaction activity cation AKD according to claim 1/alkaline sizing agent, is characterized in that, specifically comprises the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.3 hours 77 ℃ time, then add 10 grams of lauryl alcohols in 92 ℃ of reactions 2.3 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 59 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.3 hours
The 5th step, reinforced after in 84 ℃ of insulation reaction 2.6 hours,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value to 4.4, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 74 ℃, after AKD melting, stir 46 minutes, then under agitation add the deionized water of 74 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 24MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.4, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
5. the preparation method of in a kind of high reaction activity cation AKD according to claim 1/alkaline sizing agent, is characterized in that, specifically comprises the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.2 hours 78 ℃ time, then add 10 grams of lauryl alcohols in 93 ℃ of reactions 2.2 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 61 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.2 hours
The 5th step, reinforced after in 86 ℃ of insulation reaction 2.4 hours,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value to 4.6, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 76 ℃, after AKD melting, stir 44 minutes, then under agitation add the deionized water of 76 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 26MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.6, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
6. the preparation method of in a kind of high reaction activity cation AKD according to claim 1/alkaline sizing agent, is characterized in that, specifically comprises the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.1 hours 79 ℃ time, then add 10 grams of lauryl alcohols in 94 ℃ of reactions 2.1 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 63 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.1 hours
The 5th step, reinforced after in 88 ℃ of insulation reaction 2.2 hours,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value to 4.8, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 78 ℃, after AKD melting, stir 42 minutes, then under agitation add the deionized water of 78 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 28MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 4.8, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
7. the preparation method of in a kind of high reaction activity cation AKD according to claim 1/alkaline sizing agent, is characterized in that, specifically comprises the following steps:
The first step, 30 grams of OP-10 and 6 grams of maleic anhydrides are added in the first reactor and to react 1.0 hours 80 ℃ time, then add 10 grams of lauryl alcohols in 95 ℃ of reactions 2.0 hours, obtain reactive emulsifier, the mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, by 29 grams of reactive emulsifiers, 10 grams of styrene, 12 grams of methyl acrylates, 8 grams of diallylamine and 1 gram of lauryl mercaptan with mass ratio 29: 10: 12: make mixed solution at 8: 1,
The 3rd step, makes initiator solution by 2 grams of ammonium persulfates, 1 gram of sodium hydrogensulfite and 30 grams of deionized waters with mass ratio at 2: 1: 30,
The 4th step adds 159 grams of deionized waters in the second reactor, is warming up to 65 ℃, add respectively 33 grams of initiator solutions and 60 grams of mixed solutions, the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and whole feed time is 1.0 hours
The 5th step, reinforced after in 90 ℃ of insulation reaction 2.0 hours,
The 6th step, is down to room temperature, and with vinegar acid for adjusting pH value to 5, with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 125 grams of AKD emulsifying agents and 125 grams of AKD, the mass ratio of AKD emulsifying agent and AKD is 125: 125, is warming up to 80 ℃, after AKD melting, stir 40 minutes, then under agitation add the deionized water of 80 ℃ to regulate solid content to 12.5%, make the sub-stable emulsion of AKD, by sub-stable emulsion after 30MPa homogeneous, be cooled to room temperature, with vinegar acid for adjusting pH value to 5, obtain solid content and be in 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
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Effective date of registration: 20201218 Address after: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Pengbo Information Technology Co.,Ltd. Address before: 710021 Shaanxi province Xi'an Weiyang university campus of Shaanxi University of Science and Technology Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY Effective date of registration: 20201218 Address after: 224000 Qingyang Road (within Qingdun Office), Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (8) Patentee after: Yancheng Qinglong Jinbang water Co.,Ltd. Address before: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Pengbo Information Technology Co.,Ltd. |
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Correction item: Patentee|Address Correct: Yancheng Qingdun Jinbang Water Affairs Co., Ltd.|224000 Qingyang Road, Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (in Qingdun Office) (8) False: Yancheng Qingyi Jinbang Water Co., Ltd.|224000 Qingyang Road, Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (in Qingdun Office) (8) Number: 01-01 Volume: 37 |