CN102627737B - Preparation method of high-dispersion alkyl ketene dimer (AKD) neutral/alkaline sizing agent - Google Patents
Preparation method of high-dispersion alkyl ketene dimer (AKD) neutral/alkaline sizing agent Download PDFInfo
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Abstract
Provided is a preparation method of a high-dispersion alkyl ketene dimer (AKD) neutral/alkaline sizing agent. The preparation method comprises firstly performing degradation on cassava starch under the effect of fungus alpha-amylase, then enabling the degraded cassava starch to perform cationization with 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride under the effect of sodium hydroxide, and then utilizing acetic acid to achieve neutralization to obtain cation cassava starch solution. Under the effect of ammonium sulfate, the cation cassava starch solution performs graft copolymerization with methyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, acrylamide and methyl propylene acryloxyethyl trimethylammonium chloride to a copolymer with molecules containing half-crosslinking structures. The copolymer with molecules containing half-crosslinking structures is a sizing agent with excellent performance and serves as an emulsifying agent to be applied to emulsification of AKD and palm wax to obtain the high-dispersion AKD neutral/alkaline sizing agent. The prepared neutral/alkaline sizing agent emulsion particles are provided with positive charge and negative charge and have strong emulsifying and dispersing capacity. When sizing is performed under neutral/alkaline conditions, the sizing degree is remarkably improved, and the high-dispersion AKD neutral/alkaline sizing agent has good retention and sizing effects.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, the preparation method of particularly in a kind of high dispersive AKD/alkaline sizing agent.
Background technology
The major progress of modern applying glue technology be in/popularization of alkaline bleach liquor sizing technology, during acid papermaking is converted into/alkaline paper-making is the great change on world's papermaking history.In/alkaline bleach liquor sizing is in papermaking process, the pH value is adjusted to more than 7, in principle without a kind of glue applying method of Tai-Ace S 150.In commonly used/alkaline sizing agent alkyl ketene dimer (being called for short AKD) is the product of phase late 1940s research and development, AKD be a kind of can with the response type of fibrin reaction in/alkaline sizing agent, it can be as internal sizing agent, again can be as Surface Size.Its constructional feature is to be made of active group and hydrophobic grouping, the fusing point of AKD is lower, active group quaternary lactonic ring energy under the hot conditions of Dryer Section of Paper Machine in molecule and the hydroxyl reaction on Mierocrystalline cellulose form the beta-keto ester bond and are positioned on fiber, and the hydrophobic group chain alkyl produces the water resistant effect at fiber surface.By in AKD/alkaline bleach liquor sizing, the one way retention of Paper White Degree, feel, water resisting property, physical strength, printability, ageing resistance and filler etc. all is significantly improved.And can to adopt cheap water-ground limestone be filler, reduced the content of objectionable impurities in 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, reduction energy consumption, improve environmental pollution and paper machine operation performance etc., therefore can obtain obvious economic benefit and social benefit, increasing papermaking enterprise is recognized and is used in AKD/superiority and the necessity of alkaline sizing agent.China's paper making raw material is take straw pulp as main, timber resource shortage, and the secondary stock consumption increases, in utilization/the alkaline bleach liquor sizing technology has realistic meaning.Follow in 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 embodied, accelerated paper industry by acid papermaking in/trend that alkaline paper-making changes, in recent years AKD become domestic paper plant use at most, the most ripe, the most effective in/alkaline sizing agent.
In AKD/alkaline bleach liquor sizing gives paper some excellent properties, and its weak point is also arranged simultaneously.Feed ratio during according to reaction only has few part AKD that esterification has occured as can be known, and most of AKD is retained in the first reactor as blend components, does not play the effect of sizing agent.Improve in recent years and to improve the research of AKD emulsion property increasingly active, improve reactivity and the sizing efficiency of AKD emulsion, development and production has well emulsify and dispersive ability, 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 AKD/preparation method of alkaline sizing agent, in gained/alkaline sizing agent has the good emulsifying dispersive ability, 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 AKD/and the preparation method of alkaline sizing agent, comprise following concrete steps:
the first step, with water, tapioca (flour) and fungal alpha-amylase added in the first reactor in the time of 50-55 ℃ reaction 1.0-2.0 hour, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add sodium hydroxide, be warmed up to 60-70 ℃ and add the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to again 90-95 ℃ of reaction 1.0-2.0 hour, be cooled to 50-55 ℃ and add acetic acid, be down to again 20-30 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with methyl methacrylate, stearyl methacrylate and hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with acrylamide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and water by the mass ratio of 7: 4: 20,
The 4th step, ammonium persulphate and water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add cation cassava starch solution and water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65-70 ℃, add simultaneously ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.0-2.0 hour
The 6th step, reinforced complete after in 85-90 ℃ of insulation reaction 3.0-3.5 hour, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add AKD emulsifying agent, palm wax and AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85-90 ℃, after palm wax and AKD melting, stirred 40-50 minute, under agitation add the hot water of 85-90 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 25-30MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 7.5-8.5, in high dispersive AKD/alkaline sizing agent consumption 5.0-7.5Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 35-40g/m
2, tensile index 60-65 Nm/g, tear index are 7.5-8.0 mNm
2/ g, and save sizing material 20-30%.
Then the present invention first carries out cationization with the tapioca (flour) degraded, carry out graft copolymerization with acrylate again, contain half crosslinking 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 preparation/the alkaline sizing agent emulsion particle is with positive charge, have stronger emulsification and dispersive ability, 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 alkaline condition, the sizing agent that adds is dispersed between fiber, and and fiber-reactive, the arrangement that makes fiber more closely, distributing becomes very even, the fiber molecule end is introduced AKD can significantly reduce its surface energy, degree of sizing obviously improves, and has good retention and sizing efficiency.
Embodiment
The below will the present invention is described in further detail with specific embodiment.
Embodiment one
In a kind of high dispersive AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 50 ℃ reaction 1.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 60 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 90 ℃ of reactions 2.0 hours, be cooled to 50 ℃ and add 7 gram acetic acid, be down to again 20 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.0 hours
The 6th step, reinforced complete after in 85 ℃ of insulation reaction 3.5 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85 ℃, after palm wax and AKD melting, stirred 50 minutes, under agitation add the hot water of 85 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 25MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 7.5, in high dispersive AKD/alkaline sizing agent consumption 5.0Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 40 g/m
2, tensile index 60 Nm/g, tear index are 7.5 mNm
2/ g, and save sizing material 30%.
Embodiment two
In a kind of high dispersive AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 51 ℃ reaction 1.2 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 62 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 91 ℃ of reactions 1.8 hours, be cooled to 51 ℃ and add 7 gram acetic acid, be down to again 22 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 66 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.2 hours
The 6th step, reinforced complete after in 86 ℃ of insulation reaction 3.4 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 86 ℃, after palm wax and AKD melting, stirred 48 minutes, under agitation add the hot water of 86 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 26MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 7.7, in high dispersive AKD/alkaline sizing agent consumption 5.5Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 39 g/m
2, tensile index 61 Nm/g, tear index are 7.6 mNm
2/ g, and save sizing material 28%.
Embodiment three
In a kind of high dispersive AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 52 ℃ reaction 1.4 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 64 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 92 ℃ of reactions 1.6 hours, be cooled to 52 ℃ and add 7 gram acetic acid, be down to again 24 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 67 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.4 hours
The 6th step, reinforced complete after in 87 ℃ of insulation reaction 3.3 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 87 ℃, after palm wax and AKD melting, stirred 46 minutes, under agitation add the hot water of 87 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 27MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 7.9, in high dispersive AKD/alkaline sizing agent consumption 6.0Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 38 g/m
2, tensile index 62 Nm/g, tear index are 7.7 mNm
2/ g, and save sizing material 26%.
Embodiment four
In a kind of high dispersive AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 53 ℃ reaction 1.6 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 66 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 93 ℃ of reactions 1.4 hours, be cooled to 53 ℃ and add 7 gram acetic acid, be down to again 26 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 68 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.6 hours
The 6th step, reinforced complete after in 88 ℃ of insulation reaction 3.2 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 88 ℃, after palm wax and AKD melting, stirred 44 minutes, under agitation add the hot water of 88 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 28MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 8.1, in high dispersive AKD/alkaline sizing agent consumption 6.5Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 37 g/m
2, tensile index 63 Nm/g, tear index are 7.8 mNm
2/ g, and save sizing material 24%.
Embodiment five
In a kind of high dispersive AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 54 ℃ reaction 1.8 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 68 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 94 ℃ of reactions 1.2 hours, be cooled to 54 ℃ and add 7 gram acetic acid, be down to again 28 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 69 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.8 hours
The 6th step, reinforced complete after in 89 ℃ of insulation reaction 3.1 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 89 ℃, after palm wax and AKD melting, stirred 42 minutes, under agitation add the hot water of 89 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 29MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 8.3, in high dispersive AKD/alkaline sizing agent consumption 7.0Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 36 g/m
2, tensile index 64 Nm/g, tear index are 7.9 mNm
2/ g, and save sizing material 22%.
Embodiment six
In a kind of high dispersive AKD/and the preparation method of alkaline sizing agent, specifically comprise the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 55 ℃ reaction 2.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 70 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 95 ℃ of reactions 1.0 hours, be cooled to 55 ℃ and add 7 gram acetic acid, be down to again 30 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 70 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 2.0 hours
The 6th step, reinforced complete after in 90 ℃ of insulation reaction 3.0 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 90 ℃, after palm wax and AKD melting, stirred 40 minutes, under agitation add the hot water of 90 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 30MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
With in this high dispersive AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprinting paper, the pH value is 8.5, in high dispersive AKD/alkaline sizing agent consumption 7.5Kg/t paper, after applying glue, the Cobb value of newsprinting paper is 35 g/m
2, tensile index 65 Nm/g, tear index are 8.0 mNm
2/ g, and save sizing material 20%.
In sum, the present invention carries out cationization after adopting the tapioca (flour) degraded, carry out graft copolymerization with acrylate again, contain half crosslinking 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 preparation/the alkaline sizing agent emulsion particle is with positive charge, have stronger emulsification and dispersive ability, 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 alkaline condition, the sizing agent that adds is dispersed between fiber, and and fiber-reactive, make fibre array more closely, distributing becomes very even, the fiber molecule end is introduced AKD can significantly reduce its surface energy, degree of sizing obviously improves, and has good retention and sizing efficiency.
Claims (7)
1. the preparation method of in a high dispersive AKD/alkaline sizing agent is characterized in that, comprises following concrete steps:
the first step, with water, tapioca (flour) and fungal alpha-amylase added in the first reactor in the time of 50-55 ℃ reaction 1.0-2.0 hour, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add sodium hydroxide, be warmed up to 60-70 ℃ and add the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to again 90-95 ℃ of reaction 1.0-2.0 hour, be cooled to 50-55 ℃ and add acetic acid, be down to again 20-30 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with methyl methacrylate, stearyl methacrylate and hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with acrylamide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride and water by the mass ratio of 7: 4: 20,
The 4th step, ammonium persulphate and water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add cation cassava starch solution and water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65-70 ℃, add simultaneously ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.0-2.0 hour
The 6th step, reinforced complete after in 85-90 ℃ of insulation reaction 3.0-3.5 hour, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add AKD emulsifying agent, palm wax and AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85-90 ℃, after palm wax and AKD melting, stirred 40-50 minute, under agitation add the hot water of 85-90 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 25-30MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
2. the preparation method of in a kind of high dispersive AKD according to claim 1/alkaline sizing agent is characterized in that, specifically comprises the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 50 ℃ reaction 1.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 60 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 90 ℃ of reactions 2.0 hours, be cooled to 50 ℃ and add 7 gram acetic acid, be down to again 20 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 65 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.0 hours
The 6th step, reinforced complete after in 85 ℃ of insulation reaction 3.5 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 85 ℃, after palm wax and AKD melting, stirred 50 minutes, under agitation add the hot water of 85 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 25MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
3. the preparation method of in a kind of high dispersive AKD according to claim 1/alkaline sizing agent is characterized in that, specifically comprises the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 51 ℃ reaction 1.2 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 62 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 91 ℃ of reactions 1.8 hours, be cooled to 51 ℃ and add 7 gram acetic acid, be down to again 22 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 66 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.2 hours
The 6th step, reinforced complete after in 86 ℃ of insulation reaction 3.4 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 86 ℃, after palm wax and AKD melting, stirred 48 minutes, under agitation add the hot water of 86 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 26MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
4. the preparation method of in a kind of high dispersive AKD according to claim 1/alkaline sizing agent is characterized in that, specifically comprises the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 52 ℃ reaction 1.4 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 64 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 92 ℃ of reactions 1.6 hours, be cooled to 52 ℃ and add 7 gram acetic acid, be down to again 24 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 67 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.4 hours
The 6th step, reinforced complete after in 87 ℃ of insulation reaction 3.3 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 87 ℃, after palm wax and AKD melting, stirred 46 minutes, under agitation add the hot water of 87 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 27MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
5. the preparation method of in a kind of high dispersive AKD according to claim 1/alkaline sizing agent is characterized in that, specifically comprises the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 53 ℃ reaction 1.6 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 66 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 93 ℃ of reactions 1.4 hours, be cooled to 53 ℃ and add 7 gram acetic acid, be down to again 26 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 68 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.6 hours
The 6th step, reinforced complete after in 88 ℃ of insulation reaction 3.2 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 88 ℃, after palm wax and AKD melting, stirred 44 minutes, under agitation add the hot water of 88 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 28MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
6. the preparation method of in a kind of high dispersive AKD according to claim 1/alkaline sizing agent is characterized in that, specifically comprises the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 54 ℃ reaction 1.8 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 68 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 94 ℃ of reactions 1.2 hours, be cooled to 54 ℃ and add 7 gram acetic acid, be down to again 28 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 69 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 1.8 hours
The 6th step, reinforced complete after in 89 ℃ of insulation reaction 3.1 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 89 ℃, after palm wax and AKD melting, stirred 42 minutes, under agitation add the hot water of 89 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 29MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
7. the preparation method of in a kind of high dispersive AKD according to claim 1/alkaline sizing agent is characterized in that, specifically comprises the following steps:
the first step, with 200 gram water, 100 gram tapioca (flour)s and 0.6 gram fungal alpha-amylase added in the first reactor in the time of 55 ℃ reaction 2.0 hours, obtain degrading cassava starch, water, the mass ratio of tapioca (flour) and fungal alpha-amylase is 200: 100: 0.6, then add 10 gram sodium hydroxide, be warmed up to 70 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to again 95 ℃ of reactions 1.0 hours, be cooled to 55 ℃ and add 7 gram acetic acid, be down to again 30 ℃, tapioca (flour), sodium hydroxide, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, add water adjusting solid content to 25% in the first reactor, namely get cation cassava starch solution,
Second step is mixed and made into the first mix monomer with 10 gram methyl methacrylates, 18 gram stearyl methacrylates and 1 gram hydroxyethyl methylacrylate by the mass ratio of 10: 18: 1,
The 3rd step was mixed and made into the second mix monomer with 7 gram acrylamides, 4 gram MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides and 20 gram water by the mass ratio of 7: 4: 20,
The 4th step, 1 gram ammonium persulphate and 20 gram water are made ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step, add 80 gram cation cassava starch solution and 79 gram water in the second reactor, the mass ratio of cation cassava starch solution and water is 80: 79, be warming up to 70 ℃, add simultaneously 21 gram ammonium persulfate aqueous solutions, 29 gram the first mix monomers and 31 gram the second mix monomers, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, the first mix monomer and the second mix monomer is 80: 21: 29: 31, and whole feed time is 2.0 hours
The 6th step, reinforced complete after in 90 ℃ of insulation reaction 3.0 hours, then be down to room temperature, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step, add 150 gram AKD emulsifying agents, 100 gram palm waxs and 150 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 150: 100: 150, be warming up to 90 ℃, after palm wax and AKD melting, stirred 40 minutes, under agitation add the hot water of 90 ℃ to regulate solid content to 12.5%, make cation cassava starch AKD meta emulsion, with the meta emulsion after the 30MPa homogeneous, be cooled to room temperature, obtain solid content and be in 12.5% stable high dispersive AKD/alkaline sizing agent.
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