CN102635032B - Preparation method of sizing lag-free semi-crosslinked AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent - Google Patents
Preparation method of sizing lag-free semi-crosslinked AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent Download PDFInfo
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- 238000004513 sizing Methods 0.000 title claims abstract description 118
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 Alkyl Ketene Dimer Chemical compound 0.000 title abstract description 3
- 230000007935 neutral effect Effects 0.000 title abstract 4
- 240000003183 Manihot esculenta Species 0.000 claims abstract description 132
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims abstract description 132
- 229920002472 Starch Polymers 0.000 claims abstract description 95
- 239000008107 starch Substances 0.000 claims abstract description 95
- 235000019698 starch Nutrition 0.000 claims abstract description 95
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- 150000001768 cations Chemical class 0.000 claims abstract description 72
- 235000013871 bee wax Nutrition 0.000 claims abstract description 45
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 45
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 102000004139 alpha-Amylases Human genes 0.000 claims abstract description 29
- 108090000637 alpha-Amylases Proteins 0.000 claims abstract description 29
- 229940024171 alpha-amylase Drugs 0.000 claims abstract description 29
- 230000002538 fungal effect Effects 0.000 claims abstract description 29
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 112
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 103
- 239000003292 glue Substances 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 57
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 42
- 238000010792 warming Methods 0.000 claims description 42
- 239000012166 beeswax Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000013019 agitation Methods 0.000 claims description 14
- 230000000593 degrading effect Effects 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- 235000010386 dodecyl gallate Nutrition 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- CSPHGSFZFWKVDL-UHFFFAOYSA-M (3-chloro-2-hydroxypropyl)-trimethylazanium;chloride Chemical class [Cl-].C[N+](C)(C)CC(O)CCl CSPHGSFZFWKVDL-UHFFFAOYSA-M 0.000 claims description 12
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical class OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- RPWFJAMTCNSJKK-UHFFFAOYSA-N Dodecyl gallate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 RPWFJAMTCNSJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940080643 dodecyl gallate Drugs 0.000 claims description 2
- 239000000555 dodecyl gallate Substances 0.000 claims description 2
- 229940117958 vinyl acetate Drugs 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 abstract 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000000717 retained effect Effects 0.000 abstract 1
- 241000209094 Oryza Species 0.000 description 28
- 235000007164 Oryza sativa Nutrition 0.000 description 28
- 239000011436 cob Substances 0.000 description 28
- 235000009566 rice Nutrition 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 7
- 239000010791 domestic waste Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
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- 241000533901 Narcissus papyraceus Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
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- Adhesives Or Adhesive Processes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a preparation method of a sizing lag-free semi-crosslinked AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent, which comprises the steps of: firstly, carrying out degradation on the cassava starch under the action of fungal alpha-amylase; carrying out cationization on the degraded cassava starch by using 3-chloro-2-hydroxypropyltrimethyl ammonium chloride under the action of sodium hydroxide; then neutralizing by using acetic acid to obtain a cation cassava starch solution; carrying out a graft copolymerization reaction on the cation cassava starch solution, vinyl acetate, methyl methacrylate, lauryl methacrylate, acrylic acid and vinylcarbinol to obtain a copolymer which is a sizing agent with an excellent property; and emulsifying AKD and beewax by using the copolymer as an emulsifying agent to obtain the sizing lag-free semi-crosslinked AKD neutral/alkaline sizing agent. The prepared neutral/alkaline sizing agent has small emulsion viscosity and good stability; and the emulsion particle has positive charges and negative charges. Molecules of the emulsion contain semi-crosslinked groups, thus the emulsion is favorably retained and can be tightly combined with paper fibers with negative charges, thus the sizing property is improved, and the sizing lag is not caused.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, particularly a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
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 in world's papermaking history.In/alkaline bleach liquor sizing is in papermaking process, pH value is adjusted to more than 7, in principle without a kind of glue applying method of aluminum sulfate.In conventional/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 serve as internal sizing agent, can serve as again Cypres.Its design feature is to be made up of active group and hydrophobic grouping, the fusing point of AKD is lower, hydroxyl reaction on active group quaternary lactonic ring energy and cellulose under the hot conditions of Dryer Section of Paper Machine in molecule forms beta-keto ester bond and is positioned on fiber, and hydrophobic group chain alkyl produces water resistant effect at fiber surface.By in AKD/alkaline bleach liquor sizing, the one way retention of Paper White Degree, feel, WATER RESISTANCE, physical strength, printability, resistance to ag(e)ing and filler etc. is all significantly improved.And can to adopt cheap powdered whiting be filler, reduce the content of harmful substance in plain boiled water, improve the cyclic utilization rate of plain boiled water, 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., can obtain obvious economic benefit and social benefit, therefore increasing papermaking enterprise is recognized superiority and the necessity of use in AKD/alkaline sizing agent.China's paper making raw material is take straw pulp as main, timber resource shortage, and secondary stock consumption increases, in utilization/alkaline bleach liquor sizing technology has realistic meaning.Follow in AKD/alkaline bleach liquor sizing technology progressively expands 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 effectively in/alkaline sizing agent.
In AKD/alkaline bleach liquor sizing gives paper some excellent properties, also has its weak point simultaneously.AKD can continue to carry out with reacting of paper fibre within a certain period of time, and AKD applying glue not yet completes after page is dry, after batching, is still carrying out, and in 24 hours, in some weeks even thereafter, is also carrying out.Along with the prolongation of resting period, the degree of sizing of page can rise, therefore just can reach best sizing efficiency under paper roll after machine a period of time.Be prone to during this period the phenomenon that sizing efficiency goes down, and the strength character of sized paper decreases.Improve in recent years and to improve the research of AKD emulsion property increasingly active, alleviate or eliminate the phenomenon that AKD emulsion sizing efficiency goes down, it is the problem that China's papermaking researcher is made great efforts research always that development and production arrives the short and stable AKD emulsion of sizability of time of best sizing efficiency.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, in gained/alkaline sizing agent has good stability, it is stable that the water repelling property of lower machine after dryer sizing paper and strength character keep, and eliminated the phenomenon that AKD emulsion sizing efficiency goes down.
For achieving the above object, the technical solution used in the present invention is:
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, comprise following concrete steps:
The first step, by water, tapioca and fungal alpha-amylase add and in the first reactor, in the time of 50-55 ℃, react 1.0-2.0 hour, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add NaOH, be warmed up to 60-70 ℃ and add 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, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by vinylacetate, methyl methacrylate, metering system dodecyl gallate, acrylic acid and propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by ammonium persulfate and water with mass ratio at 1: 20,
The 4th step, in the second reactor, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 60-70 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.0-2.0 hour
The 5th step, reinforced after in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 6th step, cools to 30-40 ℃, and with 100-200 order net filtration, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add AKD emulsifying agent, beeswax and AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 80-85 ℃, after beeswax and AKD melting, stir 30-40 minute, under agitation add the hot water of 80-85 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 25-30MPa homogeneous, be cooled to 25-30 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 60-65 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 2.5-3.0 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 35-40 gram/meter
2, ring crush index is 7.8-8.3 ox rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 33-38 gram/meter
2, ring crush index is 7.7-8.2 ox rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 33-38 gram/meter
2, ring crush index is 7.7-8.2 ox rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 32-37 gram/meter
2, ring crush index is 7.6-8.1 ox rice
2/ gram, there is not applying glue hysteresis.
In preparation process of the present invention, do not use little molecular surface active agent, be conducive to the raising of environmental protection and effect.First then tapioca degraded is carried out to cationization, carry out graft copolymerization with acrylate again, the copolymer obtaining itself is exactly the sizing agent of excellent performance, set it as the emulsification that emulsifying agent is applied to AKD and beeswax, in preparation/alkaline sizing agent emulsion viscosity is little, good stability, emulsion particle is with positive charge and negative electrical charge, contain again half cross-linked structure simultaneously, contribute to keep and can combine closely with electronegative paper fibre, therefore greatly improved sizability, sizing efficiency is obvious, does not occur applying glue hysteresis.
The specific embodiment
Below will with specific embodiment, the present invention is described in further detail.
Embodiment mono-
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, specifically comprise the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.0 hours in the time of 50 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 60 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 20 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 60 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.0 hours
The 5th step, reinforced after in 80 ℃ of insulation reaction 3.0 hours,
The 6th step, cools to 30 ℃, and with 100 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 80 ℃, after beeswax and AKD melting, stir 30 minutes, under agitation add the hot water of 80 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 25MPa homogeneous, be cooled to 25 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 60 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 2.5 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 40 grams/meter
2, ring crush index is 7.8 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 38 grams/meter
2, ring crush index is 7.7 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 38 grams/meter
2, ring crush index is 7.7 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 37 grams/meter
2, ring crush index is 7.6 Ns of rice
2/ gram, there is not applying glue hysteresis.
Embodiment bis-
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, specifically comprise the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.2 hours in the time of 51 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 62 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 22 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 62 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.2 hours
The 5th step, reinforced after in 82 ℃ of insulation reaction 2.8 hours,
The 6th step, cools to 32 ℃, and with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 81 ℃, after beeswax and AKD melting, stir 32 minutes, under agitation add the hot water of 81 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 26MPa homogeneous, be cooled to 26 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 61 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 2.6 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 39 grams/meter
2, ring crush index is 7.9 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 37 grams/meter
2, ring crush index is 7.8 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 37 grams/meter
2, ring crush index is 7.8 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 36 grams/meter
2, ring crush index is 7.7 Ns of rice
2/ gram, there is not applying glue hysteresis.
Embodiment tri-
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, specifically comprise the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.4 hours in the time of 52 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 64 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 24 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 64 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.4 hours
The 5th step, reinforced after in 84 ℃ of insulation reaction 2.6 hours,
The 6th step, cools to 34 ℃, and with 140 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 82 ℃, after beeswax and AKD melting, stir 34 minutes, under agitation add the hot water of 82 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 27MPa homogeneous, be cooled to 27 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 62 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 2.7 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 38 grams/meter
2, ring crush index is 8.0 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 36 grams/meter
2, ring crush index is 7.9 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 36 grams/meter
2, ring crush index is 7.9 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 35 grams/meter
2, ring crush index is 7.8 Ns of rice
2/ gram, there is not applying glue hysteresis.
Embodiment tetra-
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, specifically comprise the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.6 hours in the time of 53 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 66 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 26 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 66 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.6 hours
The 5th step, reinforced after in 86 ℃ of insulation reaction 2.4 hours,
The 6th step, cools to 36 ℃, and with 160 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 83 ℃, after beeswax and AKD melting, stir 36 minutes, under agitation add the hot water of 83 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 28MPa homogeneous, be cooled to 28 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 63 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 2.8 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 37 grams/meter
2, ring crush index is 8.1 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 35 grams/meter
2, ring crush index is 8.0 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 35 grams/meter
2, ring crush index is 8.0 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 34 grams/meter
2, ring crush index is 7.9 Ns of rice
2/ gram, there is not applying glue hysteresis.
Embodiment five
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, specifically comprise the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.8 hours in the time of 54 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 68 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 28 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 68 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.8 hours
The 5th step, reinforced after in 88 ℃ of insulation reaction 2.2 hours,
The 6th step, cools to 38 ℃, and with 180 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 84 ℃, after beeswax and AKD melting, stir 38 minutes, under agitation add the hot water of 84 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 29MPa homogeneous, be cooled to 29 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 64 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 2.9 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 36 grams/meter
2, ring crush index is 8.2 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 34 grams/meter
2, ring crush index is 8.1 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 34 grams/meter
2, ring crush index is 8.1 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 33 grams/meter
2, ring crush index is 8.0 Ns of rice
2/ gram, there is not applying glue hysteresis.
Embodiment six
Without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, specifically comprise the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 2.0 hours in the time of 55 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 70 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 30 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 70 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 2.0 hours
The 5th step, reinforced after in 90 ℃ of insulation reaction 2.0 hours,
The 6th step, cools to 40 ℃, and with 200 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 85 ℃, after beeswax and AKD melting, stir 40 minutes, under agitation add the hot water of 85 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 30MPa homogeneous, be cooled to 30 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
By this without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium top sizing, starch consumption 65 kg/ton paper, without lag behind in half crosslinked AKD/alkaline sizing agent 3.0 kg/ton paper of applying glue, the Cobb value of lower machine after dryer sizing fluting medium is 35 grams/meter
2, ring crush index is 8.3 Ns of rice
2/ gram; The Cobb value of 2 hours after dryer sizing fluting mediums is 33 grams/meter
2, ring crush index is 8.2 Ns of rice
2/ gram; The Cobb value of 24 hours after dryer sizing fluting mediums is 33 grams/meter
2, ring crush index is 8.2 Ns of rice
2/ gram; The Cobb value of 7 days after dryer sizing fluting mediums is 32 grams/meter
2, ring crush index is 8.1 Ns of rice
2/ gram, there is not applying glue hysteresis.
In sum, a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue of invention gained, after adopting tapioca degraded, carry out cationization, carry out graft copolymerization with acrylate again, the copolymer obtaining itself is exactly the sizing agent of excellent performance, set it as the emulsification that emulsifying agent is applied to AKD and beeswax, in preparation/alkaline sizing agent emulsion viscosity is little, good stability, emulsion particle is with positive charge and negative electrical charge, in molecule, contain again half crosslinked group, contribute to keep and can combine closely with electronegative paper fibre, therefore greatly improved sizability, sizing efficiency is obvious, there is not applying glue hysteresis.
Claims (7)
1. without a preparation method for lag behind in half crosslinked AKD/alkaline sizing agent of applying glue, it is characterized in that, comprise following concrete steps:
The first step, by water, tapioca and fungal alpha-amylase add and in the first reactor, in the time of 50-55 ℃, react 1.0-2.0 hour, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add NaOH, be warmed up to 60-70 ℃ and add 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, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by vinylacetate, methyl methacrylate, metering system dodecyl gallate, acrylic acid and propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by ammonium persulfate and water with mass ratio at 1: 20,
The 4th step, in the second reactor, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 60-70 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.0-2.0 hour
The 5th step, reinforced after in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 6th step, cools to 30-40 ℃, and with 100-200 order net filtration, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add AKD emulsifying agent, beeswax and AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 80-85 ℃, after beeswax and AKD melting, stir 30-40 minute, under agitation add the hot water of 80-85 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 25-30MPa homogeneous, be cooled to 25-30 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
2. a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue according to claim 1, is characterized in that, specifically comprises the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.0 hours in the time of 50 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 60 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 20 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 60 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.0 hours
The 5th step, reinforced after in 80 ℃ of insulation reaction 3.0 hours,
The 6th step, cools to 30 ℃, and with 100 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 80 ℃, after beeswax and AKD melting, stir 30 minutes, under agitation add the hot water of 80 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 25MPa homogeneous, be cooled to 25 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
3. a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue according to claim 1, is characterized in that, specifically comprises the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.2 hours in the time of 51 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 62 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 22 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 62 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.2 hours
The 5th step, reinforced after in 82 ℃ of insulation reaction 2.8 hours,
The 6th step, cools to 32 ℃, and with 120 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 81 ℃, after beeswax and AKD melting, stir 32 minutes, under agitation add the hot water of 81 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 26MPa homogeneous, be cooled to 26 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
4. a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue according to claim 1, is characterized in that, specifically comprises the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.4 hours in the time of 52 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 64 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 24 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 64 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.4 hours
The 5th step, reinforced after in 84 ℃ of insulation reaction 2.6 hours,
The 6th step, cools to 34 ℃, and with 140 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 82 ℃, after beeswax and AKD melting, stir 34 minutes, under agitation add the hot water of 82 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 27MPa homogeneous, be cooled to 27 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
5. a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue according to claim 1, is characterized in that, specifically comprises the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.6 hours in the time of 53 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 66 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 26 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 66 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.6 hours
The 5th step, reinforced after in 86 ℃ of insulation reaction 2.4 hours,
The 6th step, cools to 36 ℃, and with 160 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 83 ℃, after beeswax and AKD melting, stir 36 minutes, under agitation add the hot water of 83 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 28MPa homogeneous, be cooled to 28 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
6. a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue according to claim 1, is characterized in that, specifically comprises the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 1.8 hours in the time of 54 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 68 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 28 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 68 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 1.8 hours
The 5th step, reinforced after in 88 ℃ of insulation reaction 2.2 hours,
The 6th step, cools to 38 ℃, and with 180 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 84 ℃, after beeswax and AKD melting, stir 38 minutes, under agitation add the hot water of 84 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 29MPa homogeneous, be cooled to 29 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
7. a kind of preparation method without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue according to claim 1, is characterized in that, specifically comprises the following steps:
The first step, by 200 grams of water, 100 grams of tapiocas and 0.6 gram of fungal alpha-amylase add in the first reactor and react 2.0 hours in the time of 55 ℃, obtain degrading cassava starch, water, the mass ratio of tapioca and fungal alpha-amylase is 200: 100: 0.6, then add 10 grams of NaOH, be warmed up to 70 ℃ and add 70 grams of 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 grams of acetic acid, be down to again 30 ℃, tapioca, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, regulate solid content to 25% to adding water in the first reactor, obtain cation cassava starch solution,
Second step, by 22 grams of vinylacetates, 6 grams of methyl methacrylates, 7 grams of metering system dodecyl gallates, 4 grams of acrylic acid and 1 gram of propenyl by 22: 6: 7: the mass ratio of 4: 1 is mixed and made into mix monomer,
The 3rd step, makes ammonium persulfate aqueous solution by 1 gram of ammonium persulfate and 20 grams of water with mass ratio at 1: 20,
The 4th step, in the second reactor, add 80 grams of cation cassava starch solution and 99 grams of water, the mass ratio of cation cassava starch solution and water is 80: 99, be warming up to 70 ℃, add ammonium persulfate aqueous solution and mix monomer simultaneously, the mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution and mix monomer is 80: 21: 40, and whole feed time is 2.0 hours
The 5th step, reinforced after in 90 ℃ of insulation reaction 2.0 hours,
The 6th step, cools to 40 ℃, and with 200 order net filtrations, discharging, obtains AKD emulsifying agent,
The 7th step, in the 3rd reactor, add 110 grams of AKD emulsifying agents, 80 grams of beeswaxs and 150 grams of AKD, wherein the mass ratio of AKD emulsifying agent, beeswax and AKD is 110: 80: 150, be warming up to 85 ℃, after beeswax and AKD melting, stir 40 minutes, under agitation add the hot water of 85 ℃ to regulate solid content to 15%, make the sub-stable emulsion of cation cassava starch AKD, by sub-stable emulsion after 30MPa homogeneous, be cooled to 30 ℃, obtain solid content and be 15% stable without lag behind in half crosslinked AKD/alkaline sizing agent of applying glue.
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2012
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| CN102635032A (en) | 2012-08-15 |
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Effective date of registration: 20201218 Address after: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Pengbo Information Technology Co.,Ltd. Address before: 710021 Shaanxi province Xi'an Weiyang university campus of Shaanxi University of Science and Technology Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY Effective date of registration: 20201218 Address after: 224000 Qingyang Road (within Qingdun Office), Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (8) Patentee after: Yancheng Qinglong Jinbang water Co.,Ltd. Address before: 518000 No.6 Qinglong Road, Qinglong Road, Qinghua community, Longhua street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Pengbo Information Technology Co.,Ltd. |
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Correction item: Patentee|Address Correct: Yancheng Qingdun Jinbang Water Co., Ltd.|224000 Qingyang Road, Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (in Qingdun Office) (8) False: Yancheng Qingyi Jinbang Water Co., Ltd.|224000 Qingyang Road, Nanyang Town, Tinghu District, Yancheng City, Jiangsu Province (in Qingdun Office) (8) Number: 01-01 Volume: 37 |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 |