CN102660894A - Method for preparing cation alkyl ketene dimer (AKD) neutral/alkaline sizing agent - Google Patents

Abstract

The invention discloses a method for preparing a cation alkyl ketene dimer (AKD) neutral/alkaline sizing agent. The method comprises the following steps of: preparing reactive emulsifier by using OP-10, maleic anhydride and dodecanol as raw materials; performing free radical copolymerization reaction on the reactive emulsifier, styrene, octadecyl methacrylate and di-n-butylamine ethyl butyl methacrylate by using ammonium persulfate and sodium hydrogensulfite as initiators, and isopropanol as a molecular weight regulator; and finally acidizing by using acetic acid to obtain polymer which is AKD emulsifier, AKD emulsion stabilizer and a sizing enhancement agent, and applying the polymer used as the emulsifier to emulsification of AKD to prepare neutral/alkaline sizing agent emulsion particles. The prepared neutral/alkaline sizing agent emulsion particles are positively charged under the acid condition, and are strong in emulsification and dispersing capacity and high in retention performance and sizing effect, and the sizing degree is improved obviously.

Description

A kind of preparation method of cationic AKD medium/alkaline sizing agent

technical field

The invention belongs to the field of polymer chemical sizing agents, in particular to a preparation method of cationic AKD medium/alkaline sizing agents.

Background technique

The major progress of modern sizing technology is the promotion of medium/alkaline sizing technology. The conversion of acidic papermaking to medium/alkaline papermaking is a major change in the history of papermaking in the world. Medium/alkaline sizing is a sizing method that adjusts the pH value to above 7 during the papermaking process and does not use aluminum sulfate in principle. The commonly used medium/alkaline sizing agent alkyl ketene dimer (AKD for short) is a product researched and developed in the late 1940s. AKD is a reactive medium/alkaline sizing agent that can react with cellulose , it can be used as both internal sizing agent and surface sizing agent. Its structural characteristics are composed of active groups and hydrophobic groups. The melting point of AKD is low. Under the high temperature conditions of the paper machine drying section, the active group in the molecule can react with the hydroxyl group on the cellulose to form β - The keto ester bond is positioned on the fiber, and the long-chain alkyl group of the hydrophobic group produces a water-resistant effect on the surface of the fiber. Through AKD medium/alkaline sizing, paper whiteness, hand feeling, water resistance, physical strength, printability, aging resistance and single-pass retention rate of fillers have all been significantly improved. Moreover, cheap heavy calcium carbonate can be used as filler, which reduces the content of harmful substances in white water and improves the recycling rate of white water. At the same time, the cost of AKD is lower than that of acid sizing agent. The use of AKD for medium/alkaline sizing can improve the quality and selling price of paper products, reduce energy consumption, improve environmental pollution and paper machine operation performance, etc., and can achieve obvious economic and social benefits. Therefore, more and more papermaking enterprises Recognize the superiority and necessity of using AKD medium/alkaline sizing agent. In my country, straw pulp is the main raw material for papermaking, wood resources are in short supply, and the amount of secondary fiber is increasing. It is of practical significance to use medium/alkaline sizing technology. With the gradual expansion of the application field of AKD medium/alkaline sizing technology in my country, the process technology has become increasingly mature, and the benefits of medium/alkaline papermaking have been gradually reflected, which has accelerated the trend of the paper industry from acidic papermaking to medium/alkaline papermaking. In recent years, AKD has become the most mature and effective medium/alkaline sizing agent used by domestic paper mills.

AKD medium/alkaline sizing endows paper with some excellent properties, but also has its disadvantages. AKD is unstable in water, and AKD emulsion is prone to hydrolysis and failure during preparation and storage. When the wet paper sheet is dry, AKD is in contact with water for a long time at high temperature. The reaction between AKD and fiber and the hydrolysis reaction between AKD and water compete with each other. Part of AKD fails due to hydrolysis, resulting in a decrease or lag in sizing. In recent years, the research on improving and perfecting the performance of AKD emulsion has become increasingly active, reducing the hydrolysis reaction of AKD, increasing the degree of reaction between AKD and fiber, and developing and producing AKD emulsion with good emulsion stability and high reactivity with fiber. Topics to study hard.

Contents of the invention

In order to overcome the above-mentioned shortcoming of the prior art, the object of the present invention is to provide a kind of preparation method of cationic AKD middle/alkaline sizing agent, the gained middle/alkaline sizing agent is resistant to hydrolysis, and good storage stability is arranged, It has extremely high reactivity even in the presence of water under high temperature environment, thus greatly improving the reaction efficiency and sizing effect of the rubber.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A kind of preparation method of cationic AKD medium/alkaline sizing agent, comprises the following concrete steps:

In the first step, add OP-10 and maleic anhydride to the first reactor and react at 75-80°C for 1.0-1.5 hours, then add dodecyl alcohol and react at 90-95°C for 2.0-2.5 hours to obtain reactive emulsification Agent, the mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, the reactive emulsifier, styrene, stearyl methacrylate, dibutylaminoethyl butyl methacrylate and isopropanol are mixed in a mass ratio of 29:10:8:12:1 solution,

In the third step, ammonium persulfate, sodium bisulfite and deionized water are made into an aqueous initiator solution with a mass ratio of 2: 1: 30,

The fourth step is to add deionized water to the second reactor, raise the temperature to 55-65 ° C, add the initiator aqueous solution and the mixed solution respectively, and the mass ratio of the deionized water, the initiator aqueous solution and the mixed solution is 159:33:60 , the whole feeding time is 1.0-1.5 hours,

The fifth step, after the addition is complete, keep the temperature at 80-90°C for 2.0-3.0 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 4-5 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

In the seventh step, add AKD emulsifier and AKD to the third reactor, the mass ratio of AKD emulsifier and AKD is 150:150, heat up to 70-80 ° C, after AKD melts, stir for 40-50 minutes, and then Add deionized water at 70-80°C under stirring to adjust the solid content to 12.5% to prepare an AKD metastable emulsion. Homogenize the metastable emulsion at 20-30MPa, cool to room temperature, and adjust the pH value to 4-5 with acetic acid , to obtain a stable cationic AKD medium/alkaline sizing agent with a solid content of 12.5%.

The validity period of the emulsion of the cationic AKD middle/alkaline sizing agent obtained by the present invention is extended by 60-70 days, and it is used in the pulp internal sizing of 65g/ ^m2 light paper, the pH value is 8.0-9.0, and the cationic AKD The amount of medium/alkaline sizing agent is 6.0-8.5Kg/t paper, the Cobb value of light paper after off-machine is 20-25g/m ² , and the sizing agent can be saved by 20-25%.

The invention does not use low-molecular emulsifiers in the preparation process, and the reactive emulsifiers are covalently bonded to become part of the molecular chain during the polymerization process, thereby eliminating the disadvantages caused by low-molecular emulsifiers. The obtained polymer is not only an emulsifier of AKD, but also a stabilizer and a sizing synergist of the AKD emulsion. It is used as an emulsifier for the emulsification of AKD. The prepared medium/alkaline sizing agent emulsion particles are under acidic conditions Positively charged, with strong emulsifying and dispersing ability, it can effectively emulsify and fully disperse AKD, and obtain a sizing agent emulsion with good stability. In the process of papermaking (in medium/alkaline conditions), the stabilizer fails, which is conducive to the reaction of AKD and cellulose to produce sizing. This is a great improvement on the emulsification technology of starch series AKD emulsion.

Detailed ways

The present invention will be further described in detail with specific examples below.

Embodiment one

A kind of preparation method of/alkaline sizing agent in cationic AKD, specifically comprises the following steps:

In the first step, add 30 grams of OP-10 and 6 grams of maleic anhydride into the first reactor and react at 75°C for 1.5 hours, then add 10 grams of dodecyl alcohol and react at 90°C for 2.5 hours to obtain a reactive emulsifier. The mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, 29 gram reactive emulsifiers, 10 gram styrene, 8 gram stearyl methacrylate, 12 gram dibutylaminoethyl butyl methacrylate and 1 gram isopropanol are mass ratio 29: 10:8:12:1 to make a mixed solution,

The 3rd step, 2 gram ammonium persulfate, 1 gram sodium bisulfite and 30 gram deionized water are made initiator aqueous solution with mass ratio 2: 1: 30,

In the fourth step, add 159 grams of deionized water to the second reactor, heat up to 55°C, add 33 grams of initiator aqueous solution and 60 grams of mixed solution respectively, and the mass ratio of deionized water, initiator aqueous solution and mixed solution is 159 : 33: 60, the whole feeding time is 1.5 hours,

The fifth step, after the addition is complete, keep the reaction at 80°C for 3.0 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 4 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

In the 7th step, add 150 grams of AKD emulsifier and 150 grams of AKD in the third reactor, the mass ratio of AKD emulsifier and AKD is 150: 150, be warming up to 70 ℃, after treating that AKD melts, stir 50 minutes, then in Add deionized water at 70°C under stirring to adjust the solid content to 12.5% to obtain an AKD metastable emulsion. After homogenizing the metastable emulsion at 20 MPa, cool to room temperature and adjust the pH value to 4 with acetic acid to obtain a solid content of 12.5. % Stable cationic AKD medium/alkaline sizing agent.

The validity period of the emulsion of the cationic AKD middle/alkaline sizing agent obtained by the present invention has been extended for 60 days, and it is used in the pulp internal sizing of 65g/m ² light weight paper, and the pH value is 8.0, and the cationic AKD middle/alkaline The amount of sizing agent is 6.0Kg/t paper, the Cobb value of light paper after off-machine is 25g/m ² , and the sizing agent is saved by 25%.

Embodiment two

A kind of preparation method of/alkaline sizing agent in cationic AKD, specifically comprises the following steps:

In the first step, add 30 grams of OP-10 and 6 grams of maleic anhydride into the first reactor and react at 76°C for 1.4 hours, then add 10 grams of dodecyl alcohol and react at 91°C for 2.4 hours to obtain a reactive emulsifier. The mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, 29 gram reactive emulsifiers, 10 gram styrene, 8 gram stearyl methacrylate, 12 gram dibutylaminoethyl butyl methacrylate and 1 gram isopropanol are mass ratio 29: 10:8:12:1 to make a mixed solution,

The 3rd step, 2 gram ammonium persulfate, 1 gram sodium bisulfite and 30 gram deionized water are made initiator aqueous solution with mass ratio 2: 1: 30,

In the fourth step, add 159 grams of deionized water to the second reactor, heat up to 57°C, add 33 grams of initiator aqueous solution and 60 grams of mixed solution respectively, and the mass ratio of deionized water, initiator aqueous solution and mixed solution is 159 : 33: 60, the whole feeding time is 1.4 hours,

The fifth step, after the addition is completed, the reaction is carried out at 82°C for 2.8 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 4.2 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

The 7th step, add 150 gram AKD emulsifiers and 150 gram AKDs in the 3rd reactor, the mass ratio of AKD emulsifiers and AKD is 150: 150, be warming up to 72 ℃, after treating that AKD melts, stir 48 minutes, then in Add deionized water at 72°C under stirring to adjust the solid content to 12.5% to obtain an AKD metastable emulsion. After homogenizing the metastable emulsion at 22 MPa, cool to room temperature and adjust the pH value to 4.2 with acetic acid to obtain a solid content of 12.5 % Stable cationic AKD medium/alkaline sizing agent.

The validity period of the emulsion of the cationic AKD middle/alkaline sizing agent obtained by the present invention has been extended for 62 days, and it is used in the pulp internal sizing of 65g/m ² light weight paper, and the pH value is 8.2, and the cationic AKD middle/alkaline The amount of sizing agent is 6.5Kg/t paper, the Cobb value of light paper after off-machine is 24g/m ² , and the sizing agent is saved by 24%.

Embodiment three

A kind of preparation method of/alkaline sizing agent in cationic AKD, specifically comprises the following steps:

In the first step, add 30 grams of OP-10 and 6 grams of maleic anhydride to the first reactor and react at 77°C for 1.3 hours, then add 10 grams of dodecyl alcohol and react at 92°C for 2.3 hours to obtain a reactive emulsifier. The mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, 29 gram reactive emulsifiers, 10 gram styrene, 8 gram stearyl methacrylate, 12 gram dibutylaminoethyl butyl methacrylate and 1 gram isopropanol are mass ratio 29: 10:8:12:1 to make a mixed solution,

The 3rd step, 2 gram ammonium persulfate, 1 gram sodium bisulfite and 30 gram deionized water are made initiator aqueous solution with mass ratio 2: 1: 30,

In the fourth step, add 159 grams of deionized water to the second reactor, heat up to 59 ° C, add 33 grams of initiator aqueous solution and 60 grams of mixed solution respectively, and the mass ratio of deionized water, initiator aqueous solution and mixed solution is 159 : 33: 60, the whole feeding time is 1.3 hours,

The fifth step, after the addition is completed, the reaction is carried out at 84°C for 2.6 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 4.4 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

The 7th step, add 150 gram AKD emulsifiers and 150 gram AKDs in the 3rd reactor, the mass ratio of AKD emulsifiers and AKD is 150: 150, be warming up to 74 ℃, after treating that AKD melts, stir 46 minutes, then in Add deionized water at 74°C under stirring to adjust the solid content to 12.5% to obtain an AKD metastable emulsion. After the metastable emulsion is homogenized at 24 MPa, cool to room temperature and adjust the pH value to 4.4 with acetic acid to obtain a solid content of 12.5. % Stable cationic AKD medium/alkaline sizing agent.

The validity period of the emulsion of the cationic AKD/alkaline sizing agent obtained by the present invention has been extended for 64 days, and it is used for 65g/m ² In the pulp sizing of light paper, the pH value is 8.4, and the cationic AKD/alkaline The amount of sizing agent is 7.0Kg/t paper, the Cobb value of the light paper after off-machine is 23g/m ² , and the sizing agent is saved by 23%.

Embodiment Four

A kind of preparation method of/alkaline sizing agent in cationic AKD, specifically comprises the following steps:

In the first step, add 30 grams of OP-10 and 6 grams of maleic anhydride to the first reactor and react at 78°C for 1.2 hours, then add 10 grams of dodecyl alcohol and react at 93°C for 2.2 hours to obtain a reactive emulsifier. The mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, 29 gram reactive emulsifiers, 10 gram styrene, 8 gram stearyl methacrylate, 12 gram dibutylaminoethyl butyl methacrylate and 1 gram isopropanol are mass ratio 29: 10:8:12:1 to make a mixed solution,

The 3rd step, 2 gram ammonium persulfate, 1 gram sodium bisulfite and 30 gram deionized water are made initiator aqueous solution with mass ratio 2: 1: 30,

In the fourth step, add 159 grams of deionized water to the second reactor, heat up to 61 ° C, add 33 grams of initiator aqueous solution and 60 grams of mixed solution respectively, and the mass ratio of deionized water, initiator aqueous solution and mixed solution is 159 : 33: 60, the whole feeding time is 1.2 hours,

The fifth step, after the addition is completed, the reaction is carried out at 86 ° C for 2.4 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 4.6 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

The 7th step, add 150 gram AKD emulsifiers and 150 gram AKDs in the 3rd reactor, the mass ratio of AKD emulsifiers and AKD is 150: 150, be warming up to 76 ℃, after treating that AKD melts, stir 44 minutes, then in Add deionized water at 76°C under stirring to adjust the solid content to 12.5% to obtain an AKD metastable emulsion. After homogenizing the metastable emulsion at 26 MPa, cool to room temperature and adjust the pH value to 4.6 with acetic acid to obtain a solid content of 12.5 % Stable cationic AKD medium/alkaline sizing agent.

The validity period of the emulsion of the cationic AKD middle/alkaline sizing agent obtained by the present invention has been extended for 66 days, and it is used in the pulp internal sizing of 65g/m ² light weight paper, and the pH value is 8.6, and the cationic AKD middle/alkaline The amount of sizing agent is 7.5Kg/t paper, the Cobb value of light paper after off-machine is 22g/m ² , and the sizing agent is saved by 22%.

Embodiment five

A kind of preparation method of/alkaline sizing agent in cationic AKD, specifically comprises the following steps:

In the first step, add 30 grams of OP-10 and 6 grams of maleic anhydride to the first reactor and react at 79°C for 1.1 hours, then add 10 grams of dodecyl alcohol and react at 94°C for 2.1 hours to obtain a reactive emulsifier. The mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, 29 gram reactive emulsifiers, 10 gram styrene, 8 gram stearyl methacrylate, 12 gram dibutylaminoethyl butyl methacrylate and 1 gram isopropanol are mass ratio 29: 10:8:12:1 to make a mixed solution,

The 3rd step, 2 gram ammonium persulfate, 1 gram sodium bisulfite and 30 gram deionized water are made initiator aqueous solution with mass ratio 2: 1: 30,

In the fourth step, add 159 grams of deionized water to the second reactor, heat up to 63°C, add 33 grams of initiator aqueous solution and 60 grams of mixed solution respectively, and the mass ratio of deionized water, initiator aqueous solution and mixed solution is 159 : 33: 60, the whole feeding time is 1.1 hours,

The fifth step, after the addition is complete, keep the reaction at 88°C for 2.2 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 4.8 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

The 7th step, add 150 gram AKD emulsifiers and 150 gram AKDs in the 3rd reactor, the mass ratio of AKD emulsifiers and AKD is 150: 150, be warming up to 78 ℃, after treating that AKD melts, stir 42 minutes, then in Add deionized water at 78°C under stirring to adjust the solid content to 12.5% to obtain an AKD metastable emulsion. After homogenizing the metastable emulsion at 28 MPa, cool to room temperature and adjust the pH value to 4.8 with acetic acid to obtain a solid content of 12.5 % Stable cationic AKD medium/alkaline sizing agent.

The validity period of the emulsion of the cationic AKD middle/alkaline sizing agent obtained by the present invention has been extended for 68 days, and it is used in the pulp internal sizing of 65g/m ² light weight paper, and the pH value is 8.8, and the cationic AKD middle/alkaline The amount of sizing agent is 8.0Kg/t paper, the Cobb value of the light paper after off-machine is 21g/m ² , and the sizing agent is saved by 21%.

Embodiment six

A kind of preparation method of/alkaline sizing agent in cationic AKD, specifically comprises the following steps:

In the first step, add 30 grams of OP-10 and 6 grams of maleic anhydride to the first reactor and react at 80°C for 1.0 hour, then add 10 grams of dodecyl alcohol and react at 95°C for 2.0 hours to obtain a reactive emulsifier. The mass ratio of OP-10, maleic anhydride and dodecanol is 30:6:10,

In the second step, 29 gram reactive emulsifiers, 10 gram styrene, 8 gram stearyl methacrylate, 12 gram dibutylaminoethyl butyl methacrylate and 1 gram isopropanol are mass ratio 29: 10:8:12:1 to make a mixed solution,

The 3rd step, 2 gram ammonium persulfate, 1 gram sodium bisulfite and 30 gram deionized water are made initiator aqueous solution with mass ratio 2: 1: 30,

In the fourth step, add 159 grams of deionized water to the second reactor, heat up to 65°C, add 33 grams of initiator aqueous solution and 60 grams of mixed solution respectively, and the mass ratio of deionized water, initiator aqueous solution and mixed solution is 159 :33:60, the whole feeding time is 1.0 hour,

The fifth step, after the addition is complete, keep the reaction at 90°C for 2.0 hours,

The sixth step is to drop to the greenhouse, adjust the pH value to 5 with acetic acid, filter with 120 mesh, and discharge to obtain AKD emulsifier.

In the 7th step, add 150 grams of AKD emulsifier and 150 grams of AKD in the third reactor, the mass ratio of AKD emulsifier and AKD is 150: 150, be warming up to 80 ℃, after treating that AKD melts, stir 40 minutes, then in Under stirring, add deionized water at 80°C to adjust the solid content to 12.5% to obtain an AKD metastable emulsion. After the metastable emulsion is homogenized at 30 MPa, cool to room temperature and adjust the pH value to 5 with acetic acid to obtain a solid content of 12.5. % Stable cationic AKD medium/alkaline sizing agent.

The validity period of the emulsion of the cationic AKD middle/alkaline sizing agent obtained by the present invention has been extended for 70 days, and it is used in the pulp internal sizing of 65g/ ^m2 light weight paper, and the pH value is 9.0, and the cationic AKD middle/alkaline The amount of sizing agent is 8.5Kg/t paper, the Cobb value of light paper after off-machine is 20g/m ² , and 20% of sizing material is saved.

In summary, the present invention adopts reactive emulsifier and styrene acrylate to carry out copolymerization reaction, and obtains cationic amine polymer to replace cationic starch as the emulsification stabilizer of AKD. The adaptability of positive charge is enhanced to form AKD sizing agent suitable for special wet end environment. The adjustment of the charge of the AKD emulsion particles by the amine polymer effectively reduces the tendency of hydrolysis and prolongs the validity period of the AKD emulsion. This emulsion increases the affinity between AKD molecules and cellulose hydroxyl groups and improves the retention on the fibers. AKD particles can be tightly combined with the fibers even when the paper moisture increases, so the sizing degree is significantly improved and has good properties. retention and sizing effect.

Claims (7)

1. in the cation AKD/and the preparation method of alkaline sizing agent, it is characterized in that, comprise following concrete steps:

The first step; OP-10 and maleic anhydride were added in first reactor 75-80 ℃ the time reaction 1.0-1.5 hour, add lauryl alcohol again, obtain reactive emulsifier in 90-95 ℃ of reaction 2.0-2.5 hour; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with reactive emulsifier, styrene, octadecyl methacrylate, dibutyl amino ethyl-methyl butyl acrylate and isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, ammonium persulfate, sodium hydrogensulfite and deionized water are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added deionized water in second reactor, be warming up to 55-65 ℃, added initiator solution and mixed solution respectively, and the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.0-1.5 hour,

In the 5th step, feeding in raw material finished the back in 80-90 ℃ of insulation reaction 2.0-3.0 hour,

The 6th step, reduce to the greenhouse, to 4-5, with 120 order net filtrations, discharging obtains the AKD emulsifying agent with the vinegar acid for adjusting pH value,

The 7th step added AKD emulsifying agent and AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 70-80 ℃, treat the AKD fusion after, stirred 40-50 minute; The deionized water that under agitation adds 70-80 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 20-30MPa homogeneous; Be cooled to room temperature, to 4-5, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent with the vinegar acid for adjusting pH value.

2. in a kind of cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:

The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 75 ℃ the time reaction 1.5 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 90 ℃ of reactions 2.5 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 8 gram octadecyl methacrylates, 12 gram dibutyl amino ethyl-methyl butyl acrylates and 1 gram isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added 159 gram deionized waters in second reactor, be warming up to 55 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.5 hours

In the 5th step, the reinforced back that finishes is in 80 ℃ of insulation reaction 3.0 hours,

The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,

The 7th step added 150 gram AKD emulsifying agents and 150 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 70 ℃, treat the AKD fusion after, stirred 50 minutes; The deionized water that under agitation adds 70 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 20MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent.

3. in a kind of cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:

The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 76 ℃ the time reaction 1.4 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 91 ℃ of reactions 2.4 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 8 gram octadecyl methacrylates, 12 gram dibutyl amino ethyl-methyl butyl acrylates and 1 gram isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added 159 gram deionized waters in second reactor, be warming up to 57 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.4 hours

In the 5th step, the reinforced back that finishes is in 82 ℃ of insulation reaction 2.8 hours,

The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.2, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,

The 7th step added 150 gram AKD emulsifying agents and 150 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 72 ℃, treat the AKD fusion after, stirred 48 minutes; The deionized water that under agitation adds 72 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 22MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.2, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent.

4. in a kind of cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:

The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 77 ℃ the time reaction 1.3 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 92 ℃ of reactions 2.3 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 8 gram octadecyl methacrylates, 12 gram dibutyl amino ethyl-methyl butyl acrylates and 1 gram isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added 159 gram deionized waters in second reactor, be warming up to 59 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.3 hours

In the 5th step, the reinforced back that finishes is in 84 ℃ of insulation reaction 2.6 hours,

The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.4, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,

The 7th step added 150 gram AKD emulsifying agents and 150 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 74 ℃, treat the AKD fusion after, stirred 46 minutes; The deionized water that under agitation adds 74 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 24MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.4, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent.

5. in a kind of cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:

The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 78 ℃ the time reaction 1.2 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 93 ℃ of reactions 2.2 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 8 gram octadecyl methacrylates, 12 gram dibutyl amino ethyl-methyl butyl acrylates and 1 gram isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added 159 gram deionized waters in second reactor, be warming up to 61 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.2 hours

In the 5th step, the reinforced back that finishes is in 86 ℃ of insulation reaction 2.4 hours,

The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.6, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,

The 7th step added 150 gram AKD emulsifying agents and 150 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 76 ℃, treat the AKD fusion after, stirred 44 minutes; The deionized water that under agitation adds 76 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 26MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.6, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent.

6. in a kind of cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:

The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 79 ℃ the time reaction 1.1 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 94 ℃ of reactions 2.1 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 8 gram octadecyl methacrylates, 12 gram dibutyl amino ethyl-methyl butyl acrylates and 1 gram isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added 159 gram deionized waters in second reactor, be warming up to 63 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.1 hours

In the 5th step, the reinforced back that finishes is in 88 ℃ of insulation reaction 2.2 hours,

The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.8, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,

The 7th step added 150 gram AKD emulsifying agents and 150 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 78 ℃, treat the AKD fusion after, stirred 42 minutes; The deionized water that under agitation adds 78 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 28MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.8, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent.

7. in a kind of cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:

The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 80 ℃ the time reaction 1.0 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 95 ℃ of reactions 2.0 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10

Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 8 gram octadecyl methacrylates, 12 gram dibutyl amino ethyl-methyl butyl acrylates and 1 gram isopropyl alcohol with mass ratio 29: 10: 8: process mixed solution at 12: 1,

The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,

The 4th step added 159 gram deionized waters in second reactor, be warming up to 65 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.0 hours

In the 5th step, the reinforced back that finishes is in 90 ℃ of insulation reaction 2.0 hours,

The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 5, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,

The 7th step added 150 gram AKD emulsifying agents and 150 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 150: 150; Be warming up to 80 ℃, treat the AKD fusion after, stirred 40 minutes; The deionized water that under agitation adds 80 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 30MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 5, obtain solid content and be in the 12.5% stable cation AKD/alkaline sizing agent.