CN102627734A - Preparation method of amphoteric alkyl ketene dimer (AKD) neutral/alkaline sizing agent without sizing lag - Google Patents
Preparation method of amphoteric alkyl ketene dimer (AKD) neutral/alkaline sizing agent without sizing lag Download PDFInfo
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Abstract
Provided is a preparation method of an amphoteric alkyl ketene dimer (AKD) neutral/alkaline sizing agent without sizing lag. The preparation method comprises firstly performing degradation on cassava starch under the effect of fungus alpha-amylase, then enabling the degraded cassava starch to perform cationization with 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride under the effect of sodium hydroxide, and then utilizing acetic acid to achieve neutralization to obtain cation cassava starch solution, enabling the cation cassava starch solution to perform graft copolymerization with vinyl acetate, butyl acrylate, methyl dodecyl acrylate, acrylic acid and vinylcarbinol to obtain a copolymer which is a sizing agent with excellent performance and serves as an emulsifying agent to be applied to emulsification of AKD and beewax to obtain the amphoteric alkyl ketene dimer (AKD) neutral/alkaline sizing agent without the sizing lag. The prepared neutral/alkaline sizing agent emulsion is small in viscosity and good in stability, and emulsion particles are provided with positive charge and negative charge. In addition, half-crosslinking groups are contained in molecules to facilitate retention and tight combination with paper fibers with negative charge. Therefore, the sizing performance is improved, the sizing effect is obvious, and sizing lag does not occur.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, particularly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of 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 on world's papermaking history.In/alkaline bleach liquor sizing is in papermaking process, the pH value is adjusted to more than 7, in principle without a kind of glue applying method of Tai-Ace S 150.In commonly used/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 Surface Size.Its constructional feature is to be made up of reactive group and hydrophobic grouping; The fusing point of AKD is lower; Reactive group quaternary lactonic ring ability under the hot conditions of Dryer Section of Paper Machine in the molecule and the hydroxyl reaction on the Mierocrystalline cellulose form the beta-keto ester bond and are positioned on the fiber, and the hydrophobic group chain alkyl produces anti-water effect at fiber surface.Through among the AKD/alkaline bleach liquor sizing, the one way retention of paper whiteness, feel, water resisting property, physical strength, printability, stability to aging and filler etc. all is significantly improved.And can to adopt cheap water-ground limestone be filler, reduced content of harmful in the plain boiled water, improved the cyclic utilization rate of plain boiled water, and 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, cut down the consumption of energy, improve environmental pollution and paper machine operation performance etc.; Therefore can obtain tangible economic benefit and social benefit, increasing papermaking enterprise is recognized and is used among the AKD/meliority and the necessity of alkaline sizing agent.China's paper making raw material is main with straw pulp, timber resource shortage, and the secondary stock consumption increases, in the utilization/the alkaline bleach liquor sizing technology has realistic meaning.Follow among the AKD/the alkaline bleach liquor sizing technology progressively enlarges in China's Application Areas; Technology is increasingly mature; In/benefit of alkaline paper-making progressively obtains embodying; 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.
Among the AKD/alkaline bleach liquor sizing gives paper some excellent properties, and its weak point is also arranged simultaneously.The reaction of AKD and paper fibre can continue to carry out within a certain period of time, and the AKD applying glue is not accomplished after page is done as yet, is still carrying out after batching, and is also carrying out in 24 hours even in some weeks thereafter.Along with the prolongation of shelf-time, the degree of sizing of page can rise, so machine just can reach best sizing efficiency under the paper roll after for some time.Be prone to the phenomenon that sizing efficiency goes down during this period, and the strength property of sized paper decreases.The research that improves in recent years and improve the AKD emulsion property is active day by day; Alleviate or eliminate the phenomenon that AKD emulsion sizing efficiency goes down, exploitation and to produce the short and stable AKD emulsion of sizability of the time that arrives best sizing efficiency be that China's papermaking researcher is made great efforts the problem studied always.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art; The object of the present invention is to provide does not a kind ofly have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent; In the gained/alkaline sizing agent has good stability; It is stable that the water repelling property of following machine after dryer sizing paper and strength property keep, and eliminated the phenomenon that AKD emulsion sizing efficiency goes down.
For achieving the above object, the technical scheme that the present invention adopts is:
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, comprise following concrete steps:
The first step added in first reactor drum 50-55 ℃ the time reaction 1.0-2.0 hour with water, tapioca(flour) and fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add sodium hydroxide then, be warmed up to 60-70 ℃ and add 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to 90-95 ℃ of reaction 1.0-2.0 hour again; Be cooled to 50-55 ℃ and add acetic acid; Reduce to 20-30 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second the step, with vinyl acetate, ethyl propenoate, methacrylic dodecyl gallate, vinylformic acid and vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, ammonium persulphate and water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 60-70 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.0-2.0 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 cooled to 30-40 ℃, and with 100-200 order net filtration, discharging obtains the AKD emulsifying agent,
The 7th step added AKD emulsifying agent, beeswax and AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 80-85 ℃; After treating beeswax and AKD fusion, stirred 30-40 minute, the hot water that under agitation adds 80-85 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25-30MPa homogeneous, is cooled to 25-30 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 60-65 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 2.5-3.0 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 32-37 gram/rice
2, ring crush index is a 7.5-8.0 ox rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 30-35 gram/rice
2, ring crush index is a 7.4-7.9 ox rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 30-35 gram/rice
2, ring crush index is a 7.4-7.9 ox rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 29-34 gram/rice
2, ring crush index is a 7.3-7.8 ox rice
2The applying glue hysteresis phenomenon does not appear in/gram.
The present invention prepares and does not use the small molecules tensio-active agent in the process, helps the raising of environment protection and effect.Earlier cationization is carried out in the tapioca(flour) degraded then, carry out graft copolymerization with propenoate again, the multipolymer that obtains itself is exactly the sizing agent of excellent performance; It is applied to AKD and mellisic emulsification as emulsifying agent, in the preparation/the alkaline sizing agent emulsion viscosity is little, good stability; Emulsion particle has positive charge and negative charge; Simultaneously contain half crosslinking structure again, help to keep and can combine closely, therefore improved sizability greatly with electronegative paper fibre; Sizing efficiency is obvious, the applying glue hysteresis phenomenon do not occur.
Embodiment
To be described in further detail the present invention with specific embodiment below.
Embodiment one
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor drum 50 ℃ the time reaction 1.0 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 60 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 90 ℃ of reactions 2.0 hours again; Be cooled to 50 ℃ and add 7 gram acetic acid; Reduce to 20 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 60 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.0 hours
In the 5th step, the reinforced back that finishes is in 80 ℃ of insulation reaction 3.0 hours,
The 6th step cooled to 30 ℃, and with 100 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 80 ℃; After treating beeswax and AKD fusion, stirred 30 minutes, the hot water that under agitation adds 80 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25MPa homogeneous, is cooled to 25 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 60 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 2.5 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 37 gram/rice
2, ring crush index is 7.5 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 35 gram/rice
2, ring crush index is 7.4 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 35 gram/rice
2, ring crush index is 7.4 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 34 gram/rice
2, ring crush index is 7.3 Ns of rice
2The applying glue hysteresis phenomenon does not appear in/gram.
Embodiment two
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor drum 51 ℃ the time reaction 1.2 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 62 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 91 ℃ of reactions 1.8 hours again; Be cooled to 51 ℃ and add 7 gram acetic acid; Reduce to 22 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 62 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.2 hours
In the 5th step, the reinforced back that finishes is in 82 ℃ of insulation reaction 2.8 hours,
The 6th step cooled to 32 ℃, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 81 ℃; After treating beeswax and AKD fusion, stirred 32 minutes, the hot water that under agitation adds 81 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 26MPa homogeneous, is cooled to 26 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 61 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 2.6 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 36 gram/rice
2, ring crush index is 7.6 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 34 gram/rice
2, ring crush index is 7.5 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 34 gram/rice
2, ring crush index is 7.5 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 33 gram/rice
2, ring crush index is 7.4 Ns of rice
2The applying glue hysteresis phenomenon does not appear in/gram.
Embodiment three
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor drum 52 ℃ the time reaction 1.4 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 64 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 92 ℃ of reactions 1.6 hours again; Be cooled to 52 ℃ and add 7 gram acetic acid; Reduce to 24 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 64 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.4 hours
In the 5th step, the reinforced back that finishes is in 84 ℃ of insulation reaction 2.6 hours,
The 6th step cooled to 34 ℃, and with 140 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 82 ℃; After treating beeswax and AKD fusion, stirred 34 minutes, the hot water that under agitation adds 82 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 27MPa homogeneous, is cooled to 27 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 62 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 2.7 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 35 gram/rice
2, ring crush index is 7.7 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 33 gram/rice
2, ring crush index is 7.6 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 33 gram/rice
2, ring crush index is 7.6 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 32 gram/rice
2, ring crush index is 7.5 Ns of rice
2The applying glue hysteresis phenomenon does not appear in/gram.
Embodiment four
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor drum 53 ℃ the time reaction 1.6 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 66 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 93 ℃ of reactions 1.4 hours again; Be cooled to 53 ℃ and add 7 gram acetic acid; Reduce to 26 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 66 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.6 hours
In the 5th step, the reinforced back that finishes is in 86 ℃ of insulation reaction 2.4 hours,
The 6th step cooled to 36 ℃, and with 160 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 83 ℃; After treating beeswax and AKD fusion, stirred 36 minutes, the hot water that under agitation adds 83 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 28MPa homogeneous, is cooled to 28 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 63 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 2.8 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 34 gram/rice
2, ring crush index is 7.8 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 32 gram/rice
2, ring crush index is 7.7 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 32 gram/rice
2, ring crush index is 7.7 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 31 gram/rice
2, ring crush index is 7.6 Ns of rice
2The applying glue hysteresis phenomenon does not appear in/gram.
Embodiment five
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor drum 54 ℃ the time reaction 1.8 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 68 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 94 ℃ of reactions 1.2 hours again; Be cooled to 54 ℃ and add 7 gram acetic acid; Reduce to 28 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 68 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.8 hours
In the 5th step, the reinforced back that finishes is in 88 ℃ of insulation reaction 2.2 hours,
The 6th step cooled to 38 ℃, and with 180 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 84 ℃; After treating beeswax and AKD fusion, stirred 38 minutes, the hot water that under agitation adds 84 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 29MPa homogeneous, is cooled to 29 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 64 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 2.9 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 33 gram/rice
2, ring crush index is 7.9 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 31 gram/rice
2, ring crush index is 7.8 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 31 gram/rice
2, ring crush index is 7.8 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 30 gram/rice
2, ring crush index is 7.7 Ns of rice
2The applying glue hysteresis phenomenon does not appear in/gram.
Embodiment six
A kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor drum 55 ℃ the time reaction 2.0 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 70 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 95 ℃ of reactions 1.0 hours again; Be cooled to 55 ℃ and add 7 gram acetic acid; Reduce to 30 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 70 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 2.0 hours
In the 5th step, the reinforced back that finishes is in 90 ℃ of insulation reaction 2.0 hours,
The 6th step cooled to 40 ℃, and with 200 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 85 ℃; After treating beeswax and AKD fusion, stirred 40 minutes, the hot water that under agitation adds 85 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 30MPa homogeneous, is cooled to 30 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
With among this no applying glue hysteresis both sexes AKD/alkaline sizing agent is used for the 110 gram/rice of manufacturing paper with pulp with 100% domestic waste paper
2In the Corrugating Base Paper top sizing, starch consumption 65 kg/ton paper, among the no applying glue hysteresis both sexes AKD/and alkaline sizing agent 3.0 kg/ton paper, the Cobb value of following machine after dryer sizing Corrugating Base Paper is 32 gram/rice
2, ring crush index is 8.0 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing Corrugating Base Papers is 30 gram/rice
2, ring crush index is 7.9 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing Corrugating Base Papers is 30 gram/rice
2, ring crush index is 7.9 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing Corrugating Base Papers is 29 gram/rice
2, ring crush index is 7.8 Ns of rice
2The applying glue hysteresis phenomenon does not appear in/gram.
In sum, invention gained a kind of do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, owing to carry out cationization after adopting the tapioca(flour) degraded; Carry out graft copolymerization with propenoate again, the multipolymer that obtains itself is exactly the sizing agent of excellent performance, and it is applied to AKD and mellisic emulsification as emulsifying agent; In the preparation/and the alkaline sizing agent emulsion viscosity is little, and good stability, emulsion particle have positive charge and negative charge; Contain half crosslinked group in the molecule again, help to keep and can combine closely, therefore improved sizability greatly with electronegative paper fibre; Sizing efficiency is obvious, the applying glue hysteresis phenomenon do not occur.
Claims (7)
1. one kind is not had among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, comprises following concrete steps:
The first step added in first reactor drum 50-55 ℃ the time reaction 1.0-2.0 hour with water, tapioca(flour) and fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add sodium hydroxide then, be warmed up to 60-70 ℃ and add 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to 90-95 ℃ of reaction 1.0-2.0 hour again; Be cooled to 50-55 ℃ and add acetic acid; Reduce to 20-30 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second the step, with vinyl acetate, ethyl propenoate, methacrylic dodecyl gallate, vinylformic acid and vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, ammonium persulphate and water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 60-70 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.0-2.0 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 cooled to 30-40 ℃, and with 100-200 order net filtration, discharging obtains the AKD emulsifying agent,
The 7th step added AKD emulsifying agent, beeswax and AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 80-85 ℃; After treating beeswax and AKD fusion, stirred 30-40 minute, the hot water that under agitation adds 80-85 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25-30MPa homogeneous, is cooled to 25-30 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
2. according to claim 1ly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor drum 50 ℃ the time reaction 1.0 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 60 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 90 ℃ of reactions 2.0 hours again; Be cooled to 50 ℃ and add 7 gram acetic acid; Reduce to 20 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 60 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.0 hours
In the 5th step, the reinforced back that finishes is in 80 ℃ of insulation reaction 3.0 hours,
The 6th step cooled to 30 ℃, and with 100 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 80 ℃; After treating beeswax and AKD fusion, stirred 30 minutes, the hot water that under agitation adds 80 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25MPa homogeneous, is cooled to 25 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
3. according to claim 1ly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor drum 51 ℃ the time reaction 1.2 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 62 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 91 ℃ of reactions 1.8 hours again; Be cooled to 51 ℃ and add 7 gram acetic acid; Reduce to 22 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 62 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.2 hours
In the 5th step, the reinforced back that finishes is in 82 ℃ of insulation reaction 2.8 hours,
The 6th step cooled to 32 ℃, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 81 ℃; After treating beeswax and AKD fusion, stirred 32 minutes, the hot water that under agitation adds 81 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 26MPa homogeneous, is cooled to 26 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
4. according to claim 1ly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor drum 52 ℃ the time reaction 1.4 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 64 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 92 ℃ of reactions 1.6 hours again; Be cooled to 52 ℃ and add 7 gram acetic acid; Reduce to 24 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 64 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.4 hours
In the 5th step, the reinforced back that finishes is in 84 ℃ of insulation reaction 2.6 hours,
The 6th step cooled to 34 ℃, and with 140 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 82 ℃; After treating beeswax and AKD fusion, stirred 34 minutes, the hot water that under agitation adds 82 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 27MPa homogeneous, is cooled to 27 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
5. according to claim 1ly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor drum 53 ℃ the time reaction 1.6 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 66 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 93 ℃ of reactions 1.4 hours again; Be cooled to 53 ℃ and add 7 gram acetic acid; Reduce to 26 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 66 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.6 hours
In the 5th step, the reinforced back that finishes is in 86 ℃ of insulation reaction 2.4 hours,
The 6th step cooled to 36 ℃, and with 160 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 83 ℃; After treating beeswax and AKD fusion, stirred 36 minutes, the hot water that under agitation adds 83 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 28MPa homogeneous, is cooled to 28 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
6. according to claim 1ly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor drum 54 ℃ the time reaction 1.8 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 68 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 94 ℃ of reactions 1.2 hours again; Be cooled to 54 ℃ and add 7 gram acetic acid; Reduce to 28 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 68 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 1.8 hours
In the 5th step, the reinforced back that finishes is in 88 ℃ of insulation reaction 2.2 hours,
The 6th step cooled to 38 ℃, and with 180 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 84 ℃; After treating beeswax and AKD fusion, stirred 38 minutes, the hot water that under agitation adds 84 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 29MPa homogeneous, is cooled to 29 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
7. according to claim 1ly a kind ofly do not have among the applying glue hysteresis both sexes AKD/preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor drum 55 ℃ the time reaction 2.0 hours with 200 gram water, 100 gram tapioca(flour)s and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca(flour) and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram sodium hydroxide then, be warmed up to 70 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 95 ℃ of reactions 1.0 hours again; Be cooled to 55 ℃ and add 7 gram acetic acid; Reduce to 30 ℃ again, the mass ratio of tapioca(flour), sodium hydroxide, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor drum, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
In second step, 18 gram vinyl acetates, 10 gram ethyl propenoates, 7 are restrained methacrylic dodecyl gallates, 4 gram vinylformic acid and 1 gram vinylcarbinol by 18: 10: 7: 4: 1 mass ratio is mixed and made into mix monomer,
The 3rd step, 1 gram ammonium persulphate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 4th step; In second reactor drum, add 80 gram cation cassava starch solution and 99 gram water, the mass ratio of cation cassava starch solution and water is 80: 99, is warming up to 70 ℃; Add ammonium persulfate aqueous solution and mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and the whole charging time is 2.0 hours
In the 5th step, the reinforced back that finishes is in 90 ℃ of insulation reaction 2.0 hours,
The 6th step cooled to 40 ℃, and with 200 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 110 gram AKD emulsifying agents, 80 gram beeswaxs and 150 gram AKD in the 3rd reactor drum, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150; Be warming up to 85 ℃; After treating beeswax and AKD fusion, stirred 40 minutes, the hot water that under agitation adds 85 ℃ is regulated solid content to 15%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 30MPa homogeneous, is cooled to 30 ℃, obtains solid content and be among 15% the stable no applying glue hysteresis both sexes AKD/alkaline sizing agent.
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| CN103665173A (en) * | 2013-12-31 | 2014-03-26 | 上海东升新材料有限公司 | Method for preparing high-substitution-degree cation starch emulsifier |
| CN112593450A (en) * | 2020-12-03 | 2021-04-02 | 北流市裕瑞造纸助剂有限公司 | AKD sizing agent and preparation method and application thereof |
| CN114960279A (en) * | 2022-07-12 | 2022-08-30 | 龙游富田造纸精化有限公司 | AKD production process based on dopamine modified titanium dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665173A (en) * | 2013-12-31 | 2014-03-26 | 上海东升新材料有限公司 | Method for preparing high-substitution-degree cation starch emulsifier |
| CN103665173B (en) * | 2013-12-31 | 2016-08-17 | 上海东升新材料有限公司 | The method of preparation high-substitution-decation cation starch emulsifier |
| CN112593450A (en) * | 2020-12-03 | 2021-04-02 | 北流市裕瑞造纸助剂有限公司 | AKD sizing agent and preparation method and application thereof |
| CN114960279A (en) * | 2022-07-12 | 2022-08-30 | 龙游富田造纸精化有限公司 | AKD production process based on dopamine modified titanium dioxide |
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