CN102660897B - Preparation method for highly-dispersed cationic AKD (Alkyl Ketene Dimer) as neutral/alkali sizing agent - Google Patents
Preparation method for highly-dispersed cationic AKD (Alkyl Ketene Dimer) as neutral/alkali sizing agent Download PDFInfo
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Abstract
The invention discloses a preparation method for highly-dispersed cationic AKD (Alkyl Ketene Dimer) as a neutral/alkali sizing agent. The preparation method comprises the following steps of: firstly, degrading cassava starch under the action of fungal alpha-amylase and carrying out cationization on the degraded cassava starch with 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride under the action of sodium hydroxide; secondly, neutralizing with acetic acid to obtain a cationic cassava starch solution; carrying out graft copolymerization reaction on the cationic cassava starch solution, ethyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, acrylamide and methacryloyloxyethyl-trimethyl ammonium chloride under the action of ammonium persulfate to obtain a copolymer, wherein the copolymer contains a semi-crosslinked structure; and applying the semi-crosslinked structure as an emulsifying agent to emulsification of AKD and palm wax to obtain the highly-dispersed cationic AKD as the neutral/alkali sizing agent. The emulsion particles of the prepared neutral/alkali sizing agent carry positive charges and have stronger emulsifying and dispersing capabilities; and when the sizing is carried out under the neutral/alkali conditions, the sizing degree is remarkably improved and favorable attaching property and sizing effect are obtained.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, particularly in a kind of high dispersive cation 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 aluminum sulfate.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 Cypres.Its design feature is to be made 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 the molecule and the hydroxyl reaction on the 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.By among the AKD/alkaline bleach liquor sizing, the one way retention of paper whiteness, feel, WATER RESISTANCE, physical strength, printability, resistance to ag(e)ing and filler etc. all is significantly improved.And can to adopt cheap powdered whiting 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/superiority and the necessity of alkaline sizing agent.China's paper making raw material is based on 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 effective in/alkaline sizing agent.
Among the AKD/alkaline bleach liquor sizing gives paper some excellent properties, and its weak point is also arranged simultaneously.Rate of charge during according to reaction has only few part A KD that esterification has taken place as can be known, and most of AKD is retained in first reactor as blend components, does not play the effect of sizing agent.The research that improves in recent years and improve the AKD emulsion property is active day by day, improve reactivity and the sizing efficiency of AKD emulsion, exploitation and production have well emulsify and dispersibility, and the AKD emulsion that the AKD that does not participate in reaction can be carried out effective emulsification and dispersion is 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 in a kind of high dispersive cation AKD/preparation method of alkaline sizing agent, in the gained/alkaline sizing agent has the good emulsifying dispersibility, the AKD that does not participate in reaction can be carried out fully emulsified and effective dispersion, thereby improve reaction efficiency and the sizing efficiency of sizing material.
For achieving the above object, the technical solution used in the present invention is:
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, comprise following concrete steps:
The first step, with water, tapioca and fungal alpha-amylase added in first reactor in the time of 50-55 ℃ reaction 1.0-2.0 hour, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add NaOH 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, be down to 20-30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with ethyl methacrylate, octadecyl methacrylate and hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with acrylamide, methylacryoyloxyethyl trimethyl ammonium chloride and water by 7: 4: 20 mass ratio,
The 4th step, ammonium persulfate and water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65-70 ℃, add ammonium persulfate aqueous solution, first mix monomer and second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.0-2.0 hour
In the 6th step, room temperature was down to then in 85-90 ℃ of insulation reaction 3.0-3.5 hour in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add AKD emulsifying agent, palm wax and AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85-90 ℃, after treating palm wax and AKD fusion, stirred 40-50 minute, the hot water that under agitation adds 85-90 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 25-30MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.5-8.5, in the high dispersive cation AKD/alkaline sizing agent consumption 5.0-7.5Kg/t paper, the Cobb value of newsprint is 34-39g/m after the applying glue
2, tensile index 55-60 Nm/g, tear index are 7.8-8.3 mNm
2/ g, and save sizing material 20-25%.
The present invention carries out cationization then with the tapioca degraded earlier, carry out graft copolymerization with acrylate again, contain half cross-linked structure in the copolymer molecule that obtains, it itself is exactly the sizing agent of excellent performance, it is applied to the emulsification of AKD and palm wax as emulsifying agent, in the preparation/the alkaline sizing agent emulsion particle has positive charge, have stronger emulsification and dispersibility, the AKD that does not participate in reaction can be carried out effective emulsification and dispersion, obtain sizing agent emulsion stable, good fluidity.In/when carrying out applying glue under the alkali condition, the sizing agent that adds is dispersed between the fiber, and and fiber-reactive, the arrangement that makes fiber more closely, distributing becomes very even, the terminal AKD that introduces of fiber molecule can significantly reduce its surface energy, degree of sizing obviously improves, and has good retention and sizing efficiency.
The specific embodiment
Below will the present invention is described in further detail with specific embodiment.
Embodiment one
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 50 ℃ reaction 1.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 20 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.0 hours
In the 6th step, room temperature is down to then in 85 ℃ of insulation reaction 3.5 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85 ℃, after treating palm wax and AKD fusion, stirred 50 minutes, the hot water that under agitation adds 85 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 25MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.5, in the high dispersive cation AKD/alkaline sizing agent consumption 5.0Kg/t paper, the Cobb value of newsprint is 39 g/m after the applying glue
2, tensile index 55 Nm/g, tear index are 7.8 mNm
2/ g, and save sizing material 25%.
Embodiment two
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 51 ℃ reaction 1.2 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 22 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 66 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.2 hours
In the 6th step, room temperature is down to then in 86 ℃ of insulation reaction 3.4 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 86 ℃, after treating palm wax and AKD fusion, stirred 48 minutes, the hot water that under agitation adds 86 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 26MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.7, in the high dispersive cation AKD/alkaline sizing agent consumption 5.5Kg/t paper, the Cobb value of newsprint is 38 g/m after the applying glue
2, tensile index 56 Nm/g, tear index are 7.9 mNm
2/ g, and save sizing material 24%.
Embodiment three
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 52 ℃ reaction 1.4 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 24 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 67 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.4 hours
In the 6th step, room temperature is down to then in 87 ℃ of insulation reaction 3.3 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 87 ℃, after treating palm wax and AKD fusion, stirred 46 minutes, the hot water that under agitation adds 87 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 27MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.9, in the high dispersive cation AKD/alkaline sizing agent consumption 6.0Kg/t paper, the Cobb value of newsprint is 37 g/m after the applying glue
2, tensile index 57 Nm/g, tear index are 8.0 mNm
2/ g, and save sizing material 23%.
Embodiment four
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 53 ℃ reaction 1.6 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 26 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 68 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.6 hours
In the 6th step, room temperature is down to then in 88 ℃ of insulation reaction 3.2 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 88 ℃, after treating palm wax and AKD fusion, stirred 44 minutes, the hot water that under agitation adds 88 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 28MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.1, in the high dispersive cation AKD/alkaline sizing agent consumption 6.5Kg/t paper, the Cobb value of newsprint is 36 g/m after the applying glue
2, tensile index 58 Nm/g, tear index are 8.1 mNm
2/ g, and save sizing material 22%.
Embodiment five
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 54 ℃ reaction 1.8 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 28 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 69 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.8 hours
In the 6th step, room temperature is down to then in 89 ℃ of insulation reaction 3.1 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 89 ℃, after treating palm wax and AKD fusion, stirred 42 minutes, the hot water that under agitation adds 89 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 29MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.3, in the high dispersive cation AKD/alkaline sizing agent consumption 7.0Kg/t paper, the Cobb value of newsprint is 35 g/m after the applying glue
2, tensile index 59 Nm/g, tear index are 8.2 mNm
2/ g, and save sizing material 21%.
Embodiment six
In a kind of high dispersive cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 55 ℃ reaction 2.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 70 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 2.0 hours
In the 6th step, room temperature is down to then in 90 ℃ of insulation reaction 3.0 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 90 ℃, after treating palm wax and AKD fusion, stirred 40 minutes, the hot water that under agitation adds 90 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 30MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
With in this high dispersive cation AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.5, in the high dispersive cation AKD/alkaline sizing agent consumption 7.5Kg/t paper, the Cobb value of newsprint is 34 g/m after the applying glue
2, tensile index 60 Nm/g, tear index are 8.3 mNm
2/ g, and save sizing material 20%.
In sum, the present invention carries out cationization after adopting the tapioca degraded, carry out graft copolymerization with acrylate again, contain half cross-linked structure in the copolymer molecule that obtains, it itself is exactly the sizing agent of excellent performance, it is applied to the emulsification of AKD and palm wax as emulsifying agent, in the preparation/the alkaline sizing agent emulsion particle has positive charge, have stronger emulsification and dispersibility, the AKD that does not participate in reaction can be carried out effective emulsification and dispersion, obtain sizing agent emulsion stable, good fluidity.In/when carrying out applying glue under the alkali condition, the sizing agent that adds is dispersed between the fiber, and and fiber-reactive, make fiber alignment more closely, distributing becomes very even, the terminal AKD that introduces of fiber molecule can significantly reduce its surface energy, degree of sizing obviously improves, and has good retention and sizing efficiency.
Claims (7)
1. in the high dispersive cation AKD/and the preparation method of alkaline sizing agent, it is characterized in that, comprise following concrete steps:
The first step, with water, tapioca and fungal alpha-amylase added in first reactor in the time of 50-55 ℃ reaction 1.0-2.0 hour, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add NaOH 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, be down to 20-30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with ethyl methacrylate, octadecyl methacrylate and hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with acrylamide, methylacryoyloxyethyl trimethyl ammonium chloride and water by 7: 4: 20 mass ratio,
The 4th step, ammonium persulfate and water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65-70 ℃, add ammonium persulfate aqueous solution, first mix monomer and second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.0-2.0 hour
In the 6th step, room temperature was down to then in 85-90 ℃ of insulation reaction 3.0-3.5 hour in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add AKD emulsifying agent, palm wax and AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85-90 ℃, after treating palm wax and AKD fusion, stirred 40-50 minute, the hot water that under agitation adds 85-90 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 25-30MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
2. in a kind of high dispersive 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, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 50 ℃ reaction 1.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 20 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.0 hours
In the 6th step, room temperature is down to then in 85 ℃ of insulation reaction 3.5 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85 ℃, after treating palm wax and AKD fusion, stirred 50 minutes, the hot water that under agitation adds 85 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 25MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
3. in a kind of high dispersive 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, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 51 ℃ reaction 1.2 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 22 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 66 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.2 hours
In the 6th step, room temperature is down to then in 86 ℃ of insulation reaction 3.4 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 86 ℃, after treating palm wax and AKD fusion, stirred 48 minutes, the hot water that under agitation adds 86 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 26MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
4. in a kind of high dispersive 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, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 52 ℃ reaction 1.4 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 24 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 67 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.4 hours
In the 6th step, room temperature is down to then in 87 ℃ of insulation reaction 3.3 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 87 ℃, after treating palm wax and AKD fusion, stirred 46 minutes, the hot water that under agitation adds 87 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 27MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
5. in a kind of high dispersive 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, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 53 ℃ reaction 1.6 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 26 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 68 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.6 hours
In the 6th step, room temperature is down to then in 88 ℃ of insulation reaction 3.2 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 88 ℃, after treating palm wax and AKD fusion, stirred 44 minutes, the hot water that under agitation adds 88 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 28MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
6. in a kind of high dispersive 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, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 54 ℃ reaction 1.8 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 28 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 69 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 1.8 hours
In the 6th step, room temperature is down to then in 89 ℃ of insulation reaction 3.1 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 89 ℃, after treating palm wax and AKD fusion, stirred 42 minutes, the hot water that under agitation adds 89 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 29MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
7. in a kind of high dispersive 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, with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase added in first reactor in the time of 55 ℃ reaction 2.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, add 10 gram NaOH 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, be down to 30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, in first reactor, add water adjusting solid content to 25%, namely get cation cassava starch solution
Second step was mixed and made into first mix monomer with 11 gram ethyl methacrylate, 17 gram octadecyl methacrylates and 1 gram hydroxyethyl methylacrylate by 11: 17: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, in second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 70 ℃, add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole reinforced time is 2.0 hours
In the 6th step, room temperature is down to then in 90 ℃ of insulation reaction 3.0 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 90 ℃, after treating palm wax and AKD fusion, stirred 40 minutes, the hot water that under agitation adds 90 ℃ is regulated solid content to 12.5%, make that cation cassava starch AKD is metastable to decide emulsion, decide emulsion behind the 30MPa homogeneous with metastable, be cooled to room temperature, obtain solid content and be in the 12.5% stable high dispersive cation AKD/alkaline sizing agent.
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| CN110054703B (en) * | 2019-05-08 | 2022-02-25 | 深圳市悠阳天颂科技发展有限公司 | Preparation method of enzyme-modified pregelatinized hydroxypropyl starch |
| CN110924223B (en) * | 2019-12-20 | 2022-04-08 | 济宁明升新材料有限公司 | AKD milk powder sizing agent and preparation method thereof |
| CN110983856A (en) * | 2019-12-30 | 2020-04-10 | 济宁明升新材料有限公司 | Straight-chain liquid AKD surface sizing agent and preparation method thereof |
| CN116621998A (en) * | 2023-05-08 | 2023-08-22 | 山东天成化工有限公司 | Preparation method of emulsifier for high-charge-density AKD (alkyl ketene dimer) |
| CN116444824B (en) * | 2023-06-19 | 2023-10-13 | 山东奥赛新材料有限公司 | Preparation method and application of composite cationic starch for ASA sizing agent |
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| 陈夫山等.高取代度阳离子淀粉的制备及其乳化AKD性能研究.《食品与生物技术学报》.2010,第29卷(第2期),p167-171. |
| 高取代度阳离子淀粉的制备及其乳化AKD性能研究;陈夫山等;《食品与生物技术学报》;20100331;第29卷(第2期);p167-171 * |
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