CN102635021A - Preparation method of high-reactivity cation AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent - Google Patents
Preparation method of high-reactivity cation AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent Download PDFInfo
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- 238000004513 sizing Methods 0.000 title claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- 150000001768 cations Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 Alkyl Ketene Dimer Chemical compound 0.000 title abstract description 4
- 230000007935 neutral effect Effects 0.000 title abstract 3
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 80
- 239000000839 emulsion Substances 0.000 claims abstract description 49
- 230000000694 effects Effects 0.000 claims abstract description 48
- 239000003999 initiator Substances 0.000 claims abstract description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 31
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 29
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 29
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 18
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 15
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims abstract description 15
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 90
- 239000011259 mixed solution Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 229960000583 acetic acid Drugs 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- 238000010792 warming Methods 0.000 claims description 28
- 239000003643 water by type Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 238000013019 agitation Methods 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 230000004927 fusion Effects 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 150000000211 1-dodecanols Chemical class 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000004945 emulsification Methods 0.000 abstract description 4
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000001804 emulsifying effect Effects 0.000 abstract description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 7
- 239000011436 cob Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- 235000004258 Cordia alliodora Nutrition 0.000 description 1
- 244000085692 Cordia alliodora Species 0.000 description 1
- 241000202567 Fatsia japonica Species 0.000 description 1
- 206010016590 Fibrin deposition on lens postoperative Diseases 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 239000003513 alkali Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
Abstract
The invention discloses a preparation method of a high-reactivity cation AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent, which comprises the following steps of: firstly, obtaining a reactive emulsifier by using OP-10, maleic anhydride and dodecanol as raw materials; carrying out free radical copolymerization on the reactive emulsifier, phenylethylene, methyl acrylate and acrylamine by using ammonium persulfate and sodium hydrogensulfite as initiators and using dodecanethiol as a molecular weight regulator; and finally, acidizing by using acetic acid to obtain a polymer which is an AKD emulsifier as well as an AKD emulsion stabilizer and a sizing synergist, and emulsifying the AKD by using the polymer as an emulsifying agent. The prepared neutral/alkaline sizing agent emulsion particle carries positive charges under the acidic condition, has stronger emulsification and dispersion capacities, is remarkably improved in sizing degree, and is better in retaining property and sizing effect.
Description
Technical field
The invention belongs to polymer chemistry sizing agent field, in particularly a kind of high reaction activity cation AKD/preparation method of alkaline sizing agent.
Background technology
The major progress of modern applying glue technology be in/popularization of alkaline bleach liquor sizing technology, during acid papermaking is converted into/alkaline paper-making is the great change on world's papermaking history.In/alkaline bleach liquor sizing is in papermaking process, the pH value is adjusted to more than 7, in principle without a kind of glue applying method of aluminum sulfate.In commonly used/alkaline sizing agent alkyl ketene dimer (being called for short AKD) is the product of phase late 1940s research and development; AKD be a kind of can with the response type of fibrin reaction in/alkaline sizing agent; It can be as internal sizing agent, again can be as Cypres.Its design feature is to be made up of active group and hydrophobic grouping; The fusing point of AKD is lower; Active group quaternary lactonic ring ability under the hot conditions of Dryer Section of Paper Machine in the molecule and the hydroxyl reaction on the cellulose form the beta-keto ester bond and are positioned on the fiber, and the hydrophobic group chain alkyl produces anti-water effect at fiber surface.Through among the AKD/alkaline bleach liquor sizing, the one way retention of paper whiteness, feel, WATER RESISTANCE, physical strength, printability, resistance to ag(e)ing and filler etc. all is significantly improved.And can to adopt cheap powdered whiting be filler, reduced content of harmful in the plain boiled water, improved the cyclic utilization rate of plain boiled water, and AKD is lower than the cost of acid accumulator size simultaneously.Adopt AKD carry out in/alkaline bleach liquor sizing can improve paper product quality and price, cut down the consumption of energy, improve environmental pollution and paper machine operation performance etc.; Therefore can obtain tangible economic benefit and social benefit, increasing papermaking enterprise is recognized and is used among the AKD/superiority and the necessity of alkaline sizing agent.China's paper making raw material is main with straw pulp, timber resource shortage, and the secondary stock consumption increases, in the utilization/the alkaline bleach liquor sizing technology has realistic meaning.Follow among the AKD/the alkaline bleach liquor sizing technology progressively enlarges in China's Application Areas; Technology is increasingly mature; In/benefit of alkaline paper-making progressively obtains embodying; Accelerated paper industry by acid papermaking in/trend that alkaline paper-making changes, in recent years AKD become domestic paper plant use at most, the most ripe, the most effectively in/alkaline sizing agent.
Among the AKD/alkaline bleach liquor sizing gives paper some excellent properties, and its weak point is also arranged simultaneously.AKD is unstable in water, AKD emulsion preparation and deposit in the process hydrolysis easily and lost efficacy.When the l Water Paper page or leaf was dry, the time that AKD at high temperature contact with water was longer, and AKD and fiber react the hydrolysis that carries out with AKD and water vies each other, and part A KD lost efficacy because of hydrolysis, caused degree of sizing decline or hysteresis.The research that improves in recent years and improve the AKD emulsion property is active day by day; Reduce the hydrolysis of AKD; Improve the extent of reaction of AKD and fiber, exploitation and produce good emulsion stability and with the high AKD emulsion of fiber-reactive activity be that China's papermaking researcher is made great efforts the problem studied always.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art; The object of the present invention is to provide in a kind of high reaction activity cation AKD/preparation method of alkaline sizing agent; In the gained/the alkaline sizing agent hydrolysis; Good storage stability is arranged, even there is water to exist under the hot environment high reactivity is arranged also, thereby improved the reaction efficiency and the sizing efficiency of sizing material greatly.
For achieving the above object, the technical scheme that the present invention adopts is:
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, comprise following concrete steps:
The first step; OP-10 and maleic anhydride were added in first reactor 75-80 ℃ the time reaction 1.0-1.5 hour, add lauryl alcohol again, obtain reactive emulsifier in 90-95 ℃ of reaction 2.0-2.5 hour; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with reactive emulsifier, styrene, methyl acrylate, diallylamine and lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, ammonium persulfate, sodium hydrogensulfite and deionized water are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added deionized water in second reactor, be warming up to 55-65 ℃, added initiator solution and mixed solution respectively, and the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.0-1.5 hour,
In the 5th step, feeding in raw material finished the back in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 6th step, reduce to the greenhouse, to 4-5, with 120 order net filtrations, discharging obtains the AKD emulsifying agent with the vinegar acid for adjusting pH value,
The 7th step added AKD emulsifying agent and AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 70-80 ℃, treat the AKD fusion after, stirred 40-50 minute; The deionized water that under agitation adds 70-80 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 20-30MPa homogeneous; Be cooled to room temperature, to 4-5, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent with the vinegar acid for adjusting pH value.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 70-90 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 7.5-8.5, in the high reaction activity cation AKD/alkaline sizing agent consumption 4.0-6.5Kg/t paper, the Cobb value of wood-free paper is 23-28g/m behind the following machine
2, and save sizing material 27-32%.
The present invention does not adopt low molecule emulsifying agent in the preparation process, reactive emulsifier becomes the part of strand with covalent bonds in polymerization process, thereby eliminated the weak point that low molecule emulsifying agent brings.The polymer that obtains is the emulsifying agent of AKD; Be again the stabilizing agent and the sizing synergist of AKD emulsion; It is applied to the emulsification of AKD as emulsifying agent, in the preparation/the alkaline sizing agent emulsion particle is positively charged under acid condition, has stronger emulsification and dispersibility; Can carry out effective emulsification and fully disperse AKD, obtain having the sizing agent emulsion of good stability.(in/alkali condition) stabilizing agent lost efficacy in paper-making process, helped AKD and the cellulose generation degree of sizing that reacts, and this is the improvement greatly to starch series A KD emulsion emulsifying technology.
The specific embodiment
To be described in further detail the present invention with specific embodiment below.
Embodiment one
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 75 ℃ the time reaction 1.5 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 90 ℃ of reactions 2.5 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 55 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.5 hours
In the 5th step, the reinforced back that finishes is in 80 ℃ of insulation reaction 3.0 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 70 ℃, treat the AKD fusion after, stirred 50 minutes; The deionized water that under agitation adds 70 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 20MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 70 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 7.5, in the high reaction activity cation AKD/alkaline sizing agent consumption 4.0Kg/t paper, the Cobb value of wood-free paper is 28g/m behind the following machine
2, and save sizing material 32%.
Embodiment two
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 76 ℃ the time reaction 1.4 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 91 ℃ of reactions 2.4 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 57 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.4 hours
In the 5th step, the reinforced back that finishes is in 82 ℃ of insulation reaction 2.8 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.2, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 72 ℃, treat the AKD fusion after, stirred 48 minutes; The deionized water that under agitation adds 72 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 22MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.2, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 74 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 7.7, in the high reaction activity cation AKD/alkaline sizing agent consumption 4.5Kg/t paper, the Cobb value of wood-free paper is 27g/m behind the following machine
2, and save sizing material 31%.
Embodiment three
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 77 ℃ the time reaction 1.3 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 92 ℃ of reactions 2.3 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 59 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.3 hours
In the 5th step, the reinforced back that finishes is in 84 ℃ of insulation reaction 2.6 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.4, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 74 ℃, treat the AKD fusion after, stirred 46 minutes; The deionized water that under agitation adds 74 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 24MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.4, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 78 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 7.9, in the high reaction activity cation AKD/alkaline sizing agent consumption 5.0Kg/t paper, the Cobb value of wood-free paper is 26g/m behind the following machine
2, and save sizing material 30%.
Embodiment four
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 78 ℃ the time reaction 1.2 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 93 ℃ of reactions 2.2 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 61 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.2 hours
In the 5th step, the reinforced back that finishes is in 86 ℃ of insulation reaction 2.4 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.6, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 76 ℃, treat the AKD fusion after, stirred 44 minutes; The deionized water that under agitation adds 76 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 26MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.6, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 82 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 8.1, in the high reaction activity cation AKD/alkaline sizing agent consumption 5.5Kg/t paper, the Cobb value of wood-free paper is 25g/m behind the following machine
2, and save sizing material 29%.
Embodiment five
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 79 ℃ the time reaction 1.1 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 94 ℃ of reactions 2.1 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 63 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.1 hours
In the 5th step, the reinforced back that finishes is in 88 ℃ of insulation reaction 2.2 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.8, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 78 ℃, treat the AKD fusion after, stirred 42 minutes; The deionized water that under agitation adds 78 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 28MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.8, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 86 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 8.3, in the high reaction activity cation AKD/alkaline sizing agent consumption 6.0Kg/t paper, the Cobb value of wood-free paper is 24g/m behind the following machine
2, and save sizing material 28%.
Embodiment six
In a kind of high reaction activity cation AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 80 ℃ the time reaction 1.0 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 95 ℃ of reactions 2.0 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 65 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.0 hours
In the 5th step, the reinforced back that finishes is in 90 ℃ of insulation reaction 2.0 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 5, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 80 ℃, treat the AKD fusion after, stirred 40 minutes; The deionized water that under agitation adds 80 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 30MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 5, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
In the high reaction activity cation AKD that obtains with the present invention/the emulsion extension of validity of alkaline sizing agent 90 days, use it for 70g/m
2In the plasm-glue-blending of wood-free paper, the pH value is 8.5, in the high reaction activity cation AKD/alkaline sizing agent consumption 6.5Kg/t paper, the Cobb value of wood-free paper is 23g/m behind the following machine
2, and save sizing material 27%.
In sum; The present invention adopts reactive emulsifier and styrene-acrylate to carry out copolyreaction; Obtain the cationic amine based polymer and replace the emulsion stabilizer of cationic starch as AKD; Its positive electricity density is easy to adjust, and the positive electricity adaptability of AKD micelle cohesion is strengthened, and forms the AKD sizing agent that is fit to special wet end environment.Amine polymer has reduced the hydrolysis tendency effectively to the adjustment of AKD emulsion particle electric charge, and makes the extension of validity of AKD emulsion.This emulsion has increased the affinity of AKD molecule and cellulose hydroxyl; Improvement keeping on fiber; AKD particulate even under the situation that paper moisture content increases, also can combine with fibre compact, so degree of sizing obviously improves, and has good retention and sizing efficiency.
Claims (7)
1. in the high reaction activity cation AKD/and the preparation method of alkaline sizing agent, it is characterized in that, comprise following concrete steps:
The first step; OP-10 and maleic anhydride were added in first reactor 75-80 ℃ the time reaction 1.0-1.5 hour, add lauryl alcohol again, obtain reactive emulsifier in 90-95 ℃ of reaction 2.0-2.5 hour; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with reactive emulsifier, styrene, methyl acrylate, diallylamine and lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, ammonium persulfate, sodium hydrogensulfite and deionized water are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added deionized water in second reactor, be warming up to 55-65 ℃, added initiator solution and mixed solution respectively, and the mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.0-1.5 hour,
In the 5th step, feeding in raw material finished the back in 80-90 ℃ of insulation reaction 2.0-3.0 hour,
The 6th step, reduce to the greenhouse, to 4-5, with 120 order net filtrations, discharging obtains the AKD emulsifying agent with the vinegar acid for adjusting pH value,
The 7th step added AKD emulsifying agent and AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 70-80 ℃, treat the AKD fusion after, stirred 40-50 minute; The deionized water that under agitation adds 70-80 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 20-30MPa homogeneous; Be cooled to room temperature, to 4-5, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent with the vinegar acid for adjusting pH value.
2. in a kind of high reaction activity cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 75 ℃ the time reaction 1.5 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 90 ℃ of reactions 2.5 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 55 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.5 hours
In the 5th step, the reinforced back that finishes is in 80 ℃ of insulation reaction 3.0 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 70 ℃, treat the AKD fusion after, stirred 50 minutes; The deionized water that under agitation adds 70 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 20MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
3. in a kind of high reaction activity cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 76 ℃ the time reaction 1.4 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 91 ℃ of reactions 2.4 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 57 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.4 hours
In the 5th step, the reinforced back that finishes is in 82 ℃ of insulation reaction 2.8 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.2, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 72 ℃, treat the AKD fusion after, stirred 48 minutes; The deionized water that under agitation adds 72 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 22MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.2, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
4. in a kind of high reaction activity cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 77 ℃ the time reaction 1.3 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 92 ℃ of reactions 2.3 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 59 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.3 hours
In the 5th step, the reinforced back that finishes is in 84 ℃ of insulation reaction 2.6 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.4, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 74 ℃, treat the AKD fusion after, stirred 46 minutes; The deionized water that under agitation adds 74 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 24MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.4, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
5. in a kind of high reaction activity cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 78 ℃ the time reaction 1.2 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 93 ℃ of reactions 2.2 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 61 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.2 hours
In the 5th step, the reinforced back that finishes is in 86 ℃ of insulation reaction 2.4 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.6, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 76 ℃, treat the AKD fusion after, stirred 44 minutes; The deionized water that under agitation adds 76 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 26MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.6, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
6. in a kind of high reaction activity cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 79 ℃ the time reaction 1.1 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 94 ℃ of reactions 2.1 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 63 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.1 hours
In the 5th step, the reinforced back that finishes is in 88 ℃ of insulation reaction 2.2 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 4.8, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 78 ℃, treat the AKD fusion after, stirred 42 minutes; The deionized water that under agitation adds 78 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 28MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 4.8, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
7. in a kind of high reaction activity cation AKD according to claim 1/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step; 30 gram OP-10 and 6 gram maleic anhydrides were added in first reactor 80 ℃ the time reaction 1.0 hours, add 10 gram lauryl alcohols again, obtain reactive emulsifier in 95 ℃ of reactions 2.0 hours; The mass ratio of OP-10, maleic anhydride and lauryl alcohol is 30: 6: 10
Second step, with 29 gram reactive emulsifiers, 10 gram styrene, 12 gram methyl acrylates, 8 gram diallylamine and 1 gram lauryl mercaptan with mass ratio 29: 10: 12: process mixed solution at 8: 1,
The 3rd step, 2 gram ammonium persulfates, 1 gram sodium hydrogensulfite and 30 gram deionized waters are processed initiator solution with mass ratio at 2: 1: 30,
The 4th step added 159 gram deionized waters in second reactor, be warming up to 65 ℃; Add 33 gram initiator solutions and 60 gram mixed solutions respectively; The mass ratio of deionized water, initiator solution and mixed solution is 159: 33: 60, and the whole charging time is 1.0 hours
In the 5th step, the reinforced back that finishes is in 90 ℃ of insulation reaction 2.0 hours,
The 6th step, reduce to the greenhouse, with vinegar acid for adjusting pH value to 5, with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 125 gram AKD emulsifying agents and 125 gram AKD in the 3rd reactor, the mass ratio of AKD emulsifying agent and AKD is 125: 125; Be warming up to 80 ℃, treat the AKD fusion after, stirred 40 minutes; The deionized water that under agitation adds 80 ℃ is then regulated solid content to 12.5%, makes AKD meta emulsion, with the meta emulsion behind the 30MPa homogeneous; Be cooled to room temperature, with vinegar acid for adjusting pH value to 5, obtain solid content and be in the 12.5% stable high reaction activity cation AKD/alkaline sizing agent.
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| CN104499363A (en) * | 2015-01-09 | 2015-04-08 | 广州天赐高新材料股份有限公司 | AKD emulsion and preparation method thereof |
| CN106381760A (en) * | 2016-09-16 | 2017-02-08 | 武汉市知富企业管理咨询有限公司 | Modified AKD (alkyl ketene dimer) neutral sizing agent production technique and application thereof in internal sizing |
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| CN101649584A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing surface coating reinforcing agent for secondary fibre paper |
| CN101649581A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing amphoteric high molecular base AKD emulsion |
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| CN101649584A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing surface coating reinforcing agent for secondary fibre paper |
| CN101649581A (en) * | 2009-09-01 | 2010-02-17 | 陕西科技大学 | Method for preparing amphoteric high molecular base AKD emulsion |
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| CN104499363A (en) * | 2015-01-09 | 2015-04-08 | 广州天赐高新材料股份有限公司 | AKD emulsion and preparation method thereof |
| CN106381760A (en) * | 2016-09-16 | 2017-02-08 | 武汉市知富企业管理咨询有限公司 | Modified AKD (alkyl ketene dimer) neutral sizing agent production technique and application thereof in internal sizing |
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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 Affairs 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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Granted publication date: 20140129 |