CN102635022B - Preparation method of high-activity ceresin/AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent - Google Patents
Preparation method of high-activity ceresin/AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-activity ceresin/AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent, which comprises the following steps of: firstly, carrying out oxidative degradation on cassava starch under the action of sodium hydroxide and hydrogen peroxide; then carrying out cationization on the cassava starch subjected to the oxidative degradation and 3-chloro-2-hydroxypropyltrimethyl ammonium chloride under the action of sodium hydroxide; then neutralizing by using acetic acid to obtain an amphiprotic cassava starch solution; under the action of ammonium persulfate, carrying out a graft copolymerization reaction on the amphiprotic cassava starch solution, methyl acrylate, lauryl methacrylate, styrene, acrylamide, dimethyl diallyl ammonium chloride and N-hydroxymethyl acrylamide to obtain a copolymer containing a half cross-linked structure; and finally, emulsifying AKD and ceresin by using the copolymer as an emulsifying agent to obtain the high-activity ceresin/AKD neutral/alkaline sizing agent. The prepared neutral/alkaline sizing agent emulsion has positive charges and negative charges, has stronger emulsification and dispersion capacities, is remarkably improved in sizing degree during sizing under a neutral/alkaline condition, and is better in reactivity and sizing effect.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, among particularly a kind of high activity ceresine/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., can obtain tangible economic benefit and social benefit, therefore increasing papermaking enterprise recognizes and uses 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 the reactivity and the sizing efficiency of AKD emulsion, exploitation and production have well emulsify and dispersive property, and to improve reactivity and sizing efficiency be that China's papermaking researcher is made great efforts the problem studied always thereby the AKD that does not participate in reaction can be carried out effective emulsification and dispersion.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide among a kind of high activity ceresine/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 the reactivity and the sizing efficiency of sizing material.
For achieving the above object, the technical solution used in the present invention is:
Among a kind of high activity ceresine/AKD/and the preparation method of alkaline sizing agent, comprise following concrete steps:
The first step, with water, tapioca, NaOH and hydrogen peroxide added in first reactor in the time of 80-85 ℃ reaction 1.0-1.5 hour, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add NaOH and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride then, be warming up to 90-95 ℃ of reaction 1-2 hour, be cooled to 50-55 ℃ and add acetic acid, reduce to 20-30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with methyl acrylate, metering system dodecyl gallate and styrene by 9: 13: 4 mass ratio,
The 3rd the step, with acrylamide, dimethyl diallyl ammonium chloride, N hydroxymethyl acrylamide and water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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, ceresine and AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 85-90 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.5-8.5, among high activity ceresine/AKD/alkaline sizing agent consumption 5.0-7.5Kg/t paper, the Cobb value of newsprint is 35-40g/m after the applying glue
2, tensile index 78-83 Nm/g, tear index are 6.7-7.2 mNm
2/ g, and save sizing material 20-30%.
The present invention carries out cationization again with tapioca oxidative degradation earlier, carry out graft copolymerization with acrylate then, 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 ceresine as emulsifying agent, in the preparation/the alkaline bleach liquor sizing agent emulsion is not only positively charged but also electronegative, 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 be dispersed between the fiber and and fiber-reactive, the arrangement of 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 reactivity worth and sizing efficiency.
The specific embodiment
Below will the present invention is described in further detail with specific embodiment.
Embodiment one
Among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 80 ℃ reaction 1.0 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 90 ℃ of reactions 2 hours, be cooled to 50 ℃ and add 5 gram acetic acid, reduce to 20 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, add water to first reactor and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 85 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.5, among high activity ceresine/AKD/alkaline sizing agent consumption 5.0Kg/t paper, the Cobb value of newsprint is 40 g/m after the applying glue
2, tensile index 78 Nm/g, tear index are 6.7 mNm
2/ g, and save sizing material 30%.
Embodiment two
Among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 81 ℃ reaction 1.1 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 91 ℃ of reactions 1.8 hours, be cooled to 51 ℃ and add 5 gram acetic acid, reduce to 22 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 86 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.7, among high activity ceresine/AKD/alkaline sizing agent consumption 5.5Kg/t paper, the Cobb value of newsprint is 39 g/m after the applying glue
2, tensile index 79 Nm/g, tear index are 6.8 mNm
2/ g, and save sizing material 28%.
Embodiment three
Among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 82 ℃ reaction 1.2 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 92 ℃ of reactions 1.6 hours, be cooled to 52 ℃ and add 5 gram acetic acid, reduce to 24 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, add water to first reactor and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 87 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.9, among high activity ceresine/AKD/alkaline sizing agent consumption 6.0Kg/t paper, the Cobb value of newsprint is 38 g/m after the applying glue
2, tensile index 80 Nm/g, tear index are 6.9 mNm
2/ g, and save sizing material 26%.
Embodiment four
Among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 83 ℃ reaction 1.3 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 93 ℃ of reactions 1.4 hours, be cooled to 53 ℃ and add 5 gram acetic acid, reduce to 26 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 88 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.1, among high activity ceresine/AKD/alkaline sizing agent consumption 6.5Kg/t paper, the Cobb value of newsprint is 37 g/m after the applying glue
2, tensile index 81 Nm/g, tear index are 7.0 mNm
2/ g, and save sizing material 24%.
Embodiment five
Among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 84 ℃ reaction 1.4 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 94 ℃ of reactions 1.2 hours, be cooled to 54 ℃ and add 5 gram acetic acid, reduce to 28 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 89 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.3, among high activity ceresine/AKD/alkaline sizing agent consumption 7.0Kg/t paper, the Cobb value of newsprint is 36 g/m after the applying glue
2, tensile index 82 Nm/g, tear index are 7.1 mNm
2/ g, and save sizing material 22%.
Embodiment six
Among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 85 ℃ reaction 1.5 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 95 ℃ of reactions 1 hour, be cooled to 55 ℃ and add 5 gram acetic acid, reduce to 30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 90 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
With among this high activity ceresine/AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.5, among high activity ceresine/AKD/alkaline sizing agent consumption 7.5Kg/t paper, the Cobb value of newsprint is 35 g/m after the applying glue
2, tensile index 83 Nm/g, tear index are 7.2 mNm
2/ g, and save sizing material 20%.
In sum, the present invention carries out cationization after adopting tapioca oxidative degradation, 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 ceresine as emulsifying agent, in the preparation/the alkaline bleach liquor sizing agent emulsion is not only positively charged but also electronegative, 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 be 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. among the high activity ceresine/AKD/and the preparation method of alkaline sizing agent, it is characterized in that, comprise following concrete steps:
The first step, with water, tapioca, NaOH and hydrogen peroxide added in first reactor in the time of 80-85 ℃ reaction 1.0-1.5 hour, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add NaOH and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride then, be warming up to 90-95 ℃ of reaction 1-2 hour, be cooled to 50-55 ℃ and add acetic acid, reduce to 20-30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with methyl acrylate, metering system dodecyl gallate and styrene by 9: 13: 4 mass ratio,
The 3rd the step, with acrylamide, dimethyl diallyl ammonium chloride, N hydroxymethyl acrylamide and water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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, ceresine and AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 85-90 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
2. among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 80 ℃ reaction 1.0 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 90 ℃ of reactions 2 hours, be cooled to 50 ℃ and add 5 gram acetic acid, reduce to 20 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, add water to first reactor and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 85 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
3. among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 81 ℃ reaction 1.1 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 91 ℃ of reactions 1.8 hours, be cooled to 51 ℃ and add 5 gram acetic acid, reduce to 22 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 86 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
4. among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 82 ℃ reaction 1.2 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 92 ℃ of reactions 1.6 hours, be cooled to 52 ℃ and add 5 gram acetic acid, reduce to 24 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, add water to first reactor and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 87 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
5. among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 83 ℃ reaction 1.3 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 93 ℃ of reactions 1.4 hours, be cooled to 53 ℃ and add 5 gram acetic acid, reduce to 26 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 88 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
6. among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 84 ℃ reaction 1.4 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 94 ℃ of reactions 1.2 hours, be cooled to 54 ℃ and add 5 gram acetic acid, reduce to 28 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 89 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
7. among a kind of high activity ceresine/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, 2 gram NaOH and 1 gram hydrogen peroxide added in first reactor in the time of 85 ℃ reaction 1.5 hours, obtain the oxidative degradation tapioca, water, tapioca, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, in first reactor, add 7 gram NaOH and 49 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides then, be warming up to 95 ℃ of reactions 1 hour, be cooled to 55 ℃ and add 5 gram acetic acid, reduce to 30 ℃ again, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5, in first reactor, add water and regulate solid content to 25%, promptly get both sexes tapioca solution
Second step was mixed and made into first mix monomer with 9 gram methyl acrylates, 13 gram metering system dodecyl gallates and 4 gram styrene by 9: 13: 4 mass ratio,
In the 3rd step, 7 gram acrylamides, 5 gram dimethyl diallyl ammonium chlorides, 2 gram N hydroxymethyl acrylamides and 20 are restrained water by 7: 5: 2: 20 mass ratio is mixed and made into second mix monomer,
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 both sexes tapioca solution and 79 gram water, the mass ratio of both sexes tapioca 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 both sexes tapioca 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 reduced 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 145 gram AKD emulsifying agents, 110 gram ceresine and 145 gram AKD, wherein the mass ratio of AKD emulsifying agent, ceresine and AKD is 145: 110: 145, be warming up to 90 ℃, after treating ceresine 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 among 12.5% stable high activity ceresine/AKD/alkaline sizing agent.
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| CN101168940A (en) * | 2007-12-04 | 2008-04-30 | 天津科技大学 | Method for preparing paraffin/AKD composite neutral paper-making glue blending agent |
| CN101302320A (en) * | 2008-06-06 | 2008-11-12 | 陕西科技大学 | Preparation of cation polymer emulsifier for AKD |
| CN102337707A (en) * | 2011-09-29 | 2012-02-01 | 浙江展航生物科技有限公司 | Preparation method of modified AKD (Alkyl Ketene Dimer) neutral sizing agent |
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| CN101168940A (en) * | 2007-12-04 | 2008-04-30 | 天津科技大学 | Method for preparing paraffin/AKD composite neutral paper-making glue blending agent |
| CN101302320A (en) * | 2008-06-06 | 2008-11-12 | 陕西科技大学 | Preparation of cation polymer emulsifier for AKD |
| CN102337707A (en) * | 2011-09-29 | 2012-02-01 | 浙江展航生物科技有限公司 | Preparation method of modified AKD (Alkyl Ketene Dimer) neutral sizing agent |
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