CN102635035B - Preparation method of amphiprotic potato starch AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent - Google Patents
Preparation method of amphiprotic potato starch AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent Download PDFInfo
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- 229920001592 potato starch Polymers 0.000 title claims abstract description 174
- 238000004513 sizing Methods 0.000 title claims abstract description 77
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 Alkyl Ketene Dimer Chemical compound 0.000 title abstract description 3
- 230000007935 neutral effect Effects 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 171
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000012188 paraffin wax Substances 0.000 claims abstract description 80
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 48
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- 238000010525 oxidative degradation reaction Methods 0.000 claims abstract description 18
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 14
- 230000033228 biological regulation Effects 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 230000000630 rising effect Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010792 warming 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
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 abstract description 5
- 229920002261 Corn starch Polymers 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000008120 corn starch Substances 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 19
- 244000085692 Cordia alliodora Species 0.000 description 8
- 235000004258 Cordia alliodora Nutrition 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 241000209094 Oryza Species 0.000 description 7
- 235000007164 Oryza sativa Nutrition 0.000 description 7
- 239000011436 cob Substances 0.000 description 7
- 239000010791 domestic waste Substances 0.000 description 7
- 235000009566 rice Nutrition 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
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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
- 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 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
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of an amphiprotic potato starch AKD (Alkyl Ketene Dimer) neutral/alkaline sizing agent, which comprises the following steps of: firstly, carrying out oxidative degradation on the potato starch under the action of hydrogen peroxide; carrying out cationization on the potato starch subjected to the oxidative degradation by using 3-chloro-2-hydroxypropyltrimethyl ammonium chloride under the action of sodium hydroxide; then neutralizing by using acetic acid to obtain an amphiprotic potato starch emulsifier; and finally emulsifying the AKD and paraffin wax by using the amphiprotic corn starch emulsifier to obtain the amphiprotic potato starch AKD neutral/alkaline sizing agent. The prepared amphiprotic potato starch AKD neutral/alkaline sizing agent has positive charges and negative charges and is beneficial to tight combination with paper fibers, thus the sizing property is greatly improved. According to the invention, in a preparation process, amphiprotic potato starch with low price is used as the emulsifier, and the paraffin wax with low price is used for replacing partial AKD with higher price, thus the stabilization property and sizing property of emulsion are improved, and the sizing cost is lowered.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, the preparation method of particularly in a kind of both sexes potato starch AKD/alkaline sizing agent.
Background technology
The major progress of modern applying glue technology be in/popularization of alkaline bleach liquor sizing technology, during acid papermaking is converted into/alkaline paper-making is the great change 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.Tradition AKD emulsion adopts the emulsifying agent of cassava cationic starch as AKD, and tapioca purity is high, and gelatinization point is low, sticks with paste liquid good fluidity, and transparency is high, a little less than retrogradation, be difficult for layering.But its price is higher, the AKD emulsion price making is thus higher, and the market competitiveness is poor.Improve in recent years and to improve the research of AKD emulsion property increasingly active, improve the market competitiveness of AKD, in development and production excellent performance, low-cost AKD/alkaline bleach liquor sizing is the problem that China's papermaking researcher is made great efforts research always.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the preparation method of the object of the present invention is to provide in a kind of both sexes potato starch AKD/alkaline sizing agent, in the AKD of gained/alkaline sizing agent has good stability, can improve degree of sizing and the surface strength of paper, and reduce applying glue cost.
For achieving the above object, the technical solution used in the present invention is:
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by water, potato starch, NaOH and hydrogen peroxide add and in the first reactor, in the time of 80-85 ℃, react 1.0-1.5 hour, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to 90-95 ℃ of reaction 1-2 hour, be cooled to 50-55 ℃ and add acetic acid, be down to again 20-30 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content, to 20-25%, obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add both sexes potato starch emulsifying agent, paraffin and AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature is to 70-75 ℃, after paraffin and AKD melting, stir 30-40 minute, under agitation add the hot water of 75-80 ℃ to disperse to be adjusted to solid content to 15-20%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 20-30MPa homogeneous, be cooled to 25-30 ℃, obtain solid content and be in the stable both sexes potato starch AKD of 15-20%/alkaline sizing agent, described paraffin is semi-refined paraffin wax or fully refined paraffin wax, or both are with the mixture of arbitrary proportion.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 65-70 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.0-3.5 kg/ton paper, after Cypres, the Cobb value of fluting medium is 33-38 gram/meter
2, ring crush index is 7.5-8.0 ox rice
2/ gram, fracture length is 4.3-4.8 km, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 7-12 unit.
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 potato starch oxidative degradation carried out to cationization, set it as emulsifying agent and be applied to the emulsification of AKD and paraffin, in preparation/alkaline sizing agent emulsion viscosity is little, good stability.The emulsion particle of preparation is not only positively charged but also electronegative, contributes to keep and can combine closely with electronegative paper fibre, not only improves emulsion-stabilizing performance and sizability, and has reduced applying glue cost.
The specific embodiment
Below will with specific embodiment, the present invention is described in further detail.
Embodiment mono-
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.0 hours in the time of 80 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 90 ℃ of reactions 2 hours, be cooled to 50 ℃ and add 5 grams of acetic acid, be down to again 20 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 20% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 70 ℃, after paraffin and AKD melting, stir 40 minutes, under agitation add the hot water of 75 ℃ to disperse to be adjusted to solid content to 15%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 20MPa homogeneous, be cooled to 25 ℃, obtain solid content and be in 15% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 65 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.0 kg/ton paper, after Cypres, the Cobb value of fluting medium is 38 grams/meter
2, ring crush index is 7.5 Ns of rice
2/ gram, fracture length is 4.5 kms, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 12 yuan.
Embodiment bis-
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.1 hours in the time of 81 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 91 ℃ of reactions 1.8 hours, be cooled to 51 ℃ and add 5 grams of acetic acid, be down to again 22 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 21% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 71 ℃, after paraffin and AKD melting, stir 38 minutes, under agitation add the hot water of 76 ℃ to disperse to be adjusted to solid content to 16%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 22MPa homogeneous, be cooled to 26 ℃, obtain solid content and be in 16% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is fully refined paraffin wax.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 66 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.1 kg/ton paper, after Cypres, the Cobb value of fluting medium is 37 grams/meter
2, ring crush index is 7.6 Ns of rice
2/ gram, fracture length is 4.6 kms, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 11 yuan.
Embodiment tri-
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.2 hours in the time of 82 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 92 ℃ of reactions 1.6 hours, be cooled to 52 ℃ and add 5 grams of acetic acid, be down to again 24 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 22% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 72 ℃, after paraffin and AKD melting, stir 36 minutes, under agitation add the hot water of 77 ℃ to disperse to be adjusted to solid content to 17%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 24MPa homogeneous, be cooled to 27 ℃, obtain solid content and be in 17% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 67 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.2 kg/ton paper, after Cypres, the Cobb value of fluting medium is 36 grams/meter
2, ring crush index is 7.7 Ns of rice
2/ gram, fracture length is 4.7 kms, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 10 yuan.
Embodiment tetra-
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.3 hours in the time of 83 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 93 ℃ of reactions 1.4 hours, be cooled to 53 ℃ and add 5 grams of acetic acid, be down to again 26 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 23% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 73 ℃, after paraffin and AKD melting, stir 34 minutes, under agitation add the hot water of 78 ℃ to disperse to be adjusted to solid content to 18%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 26MPa homogeneous, be cooled to 28 ℃, obtain solid content and be in 18% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is fully refined paraffin wax.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 68 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.3 kg/ton paper, after Cypres, the Cobb value of fluting medium is 35 grams/meter
2, ring crush index is 7.8 Ns of rice
2/ gram, fracture length is 4.8 kms, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 9 yuan.
Embodiment five
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.4 hours in the time of 84 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 94 ℃ of reactions 1.2 hours, be cooled to 54 ℃ and add 5 grams of acetic acid, be down to again 28 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 24% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 74 ℃, after paraffin and AKD melting, stir 32 minutes, under agitation add the hot water of 79 ℃ to disperse to be adjusted to solid content to 19%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 28MPa homogeneous, be cooled to 29 ℃, obtain solid content and be in 19% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax and fully refined paraffin wax mixture, both mass ratioes are 2: 1.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 69 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.4 kg/ton paper, after Cypres, the Cobb value of fluting medium is 34 grams/meter
2, ring crush index is 7.9 Ns of rice
2/ gram, fracture length is 4.8 kms, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 8 yuan.
Embodiment six
In both sexes potato starch AKD/and the preparation method of alkaline sizing agent, comprise the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.5 hours in the time of 85 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 95 ℃ of reactions 1 hour, be cooled to 55 ℃ and add 5 grams of acetic acid, be down to again 30 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 25% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 75 ℃, after paraffin and AKD melting, stir 30 minutes, under agitation add the hot water of 80 ℃ to disperse to be adjusted to solid content to 20%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 30MPa homogeneous, be cooled to 30 ℃, obtain solid content and be in 20% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax and fully refined paraffin wax mixture, both mass ratioes are 1: 2.
By in this both sexes potato starch AKD/alkaline sizing agent is for 110 grams/meter of manufacturing paper with pulp with 100% domestic waste paper
2in fluting medium, starch consumption 70 kg/ton paper, in both sexes potato starch AKD/and alkaline sizing agent 3.5 kg/ton paper, after Cypres, the Cobb value of fluting medium is 33 grams/meter
2, ring crush index is 8.0 Ns of rice
2/ gram, fracture length is 4.8 kms, reaches A level high-strength corrugated base paper QUALITY STANDARD, with in both sexes potato starches AKD/alkaline sizing agent applying glue after, the applying glue cost of fluting medium per ton 7 yuan.
In sum, the present invention carries out cationization after adopting potato starch oxidative degradation, set it as the emulsification that emulsifying agent is applied to AKD and paraffin, in preparation/alkaline sizing agent emulsion viscosity is little, good stability, the emulsion particle of preparation is not only positively charged but also electronegative, contributes to keep and can combine closely with electronegative paper fibre, not only improve emulsion-stabilizing performance and sizability, and reduced applying glue cost.
Claims (7)
1. a preparation method in both sexes potato starch AKD/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by water, potato starch, NaOH and hydrogen peroxide add and in the first reactor, in the time of 80-85 ℃, react 1.0-1.5 hour, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to 90-95 ℃ of reaction 1-2 hour, be cooled to 50-55 ℃ and add acetic acid, be down to again 20-30 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content, to 20-25%, obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add both sexes potato starch emulsifying agent, paraffin and AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature is to 70-75 ℃, after paraffin and AKD melting, stir 30-40 minute, under agitation add the hot water of 75-80 ℃ to disperse to be adjusted to solid content to 15-20%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 20-30MPa homogeneous, be cooled to 25-30 ℃, obtain solid content and be in the stable both sexes potato starch AKD of 15-20%/alkaline sizing agent, described paraffin is semi-refined paraffin wax or fully refined paraffin wax, or both are with the mixture of arbitrary proportion.
2. the preparation method of in a kind of both sexes potato starch AKD according to claim 1/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.0 hours in the time of 80 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 90 ℃ of reactions 2 hours, be cooled to 50 ℃ and add 5 grams of acetic acid, be down to again 20 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 20% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 70 ℃, after paraffin and AKD melting, stir 40 minutes, under agitation add the hot water of 75 ℃ to disperse to be adjusted to solid content to 15%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 20MPa homogeneous, be cooled to 25 ℃, obtain solid content and be in 15% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax.
3. the preparation method of in a kind of both sexes potato starch AKD according to claim 1/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.1 hours in the time of 81 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 91 ℃ of reactions 1.8 hours, be cooled to 51 ℃ and add 5 grams of acetic acid, be down to again 22 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 21% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 71 ℃, after paraffin and AKD melting, stir 38 minutes, under agitation add the hot water of 76 ℃ to disperse to be adjusted to solid content to 16%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 22MPa homogeneous, be cooled to 26 ℃, obtain solid content and be in 16% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is fully refined paraffin wax.
4. the preparation method of in a kind of both sexes potato starch AKD according to claim 1/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.2 hours in the time of 82 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 92 ℃ of reactions 1.6 hours, be cooled to 52 ℃ and add 5 grams of acetic acid, be down to again 24 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 22% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 72 ℃, after paraffin and AKD melting, stir 36 minutes, under agitation add the hot water of 77 ℃ to disperse to be adjusted to solid content to 17%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 24MPa homogeneous, be cooled to 27 ℃, obtain solid content and be in 17% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax.
5. the preparation method of in a kind of both sexes potato starch AKD according to claim 1/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.3 hours in the time of 83 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 93 ℃ of reactions 1.4 hours, be cooled to 53 ℃ and add 5 grams of acetic acid, be down to again 26 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 23% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 73 ℃, after paraffin and AKD melting, stir 34 minutes, under agitation add the hot water of 78 ℃ to disperse to be adjusted to solid content to 18%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 26MPa homogeneous, be cooled to 28 ℃, obtain solid content and be in 18% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is fully refined paraffin wax.
6. the preparation method of in a kind of both sexes potato starch AKD according to claim 1/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.4 hours in the time of 84 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 94 ℃ of reactions 1.2 hours, be cooled to 54 ℃ and add 5 grams of acetic acid, be down to again 28 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 24% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 74 ℃, after paraffin and AKD melting, stir 32 minutes, under agitation add the hot water of 79 ℃ to disperse to be adjusted to solid content to 19%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 28MPa homogeneous, be cooled to 29 ℃, obtain solid content and be in 19% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax and fully refined paraffin wax mixture, both mass ratioes are 2: 1.
7. the preparation method of in a kind of both sexes potato starch AKD according to claim 1/alkaline sizing agent, is characterized in that, comprises the following steps:
The first step, by 200 grams of water, 100 grams of potato starches, 2 grams of NaOH and 1 gram of hydrogen peroxide add in the first reactor and react 1.5 hours in the time of 85 ℃, obtain oxidative degradation potato starch, water, potato starch, the mass ratio of NaOH and hydrogen peroxide is 200: 100: 2: 1, then in the first reactor, add NaOH and 49 grams of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 95 ℃ of reactions 1 hour, be cooled to 55 ℃ and add 5 grams of acetic acid, be down to again 30 ℃, potato starch, NaOH, the mass ratio of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 7: 49: 5,
Second step adds water in the first reactor, and regulation system solid content to 25% obtains both sexes potato starch emulsifying agent,
The 3rd step, in the second reactor, add 120 grams of both sexes potato starch emulsifying agents, 120 grams of paraffin and 100 grams of AKD, wherein both sexes potato starch emulsifying agent, the mass ratio of paraffin and AKD is 120: 120: 100, rising temperature to 75 ℃, after paraffin and AKD melting, stir 30 minutes, under agitation add the hot water of 80 ℃ to disperse to be adjusted to solid content to 20%, make the sub-stable emulsion of both sexes potato starch AKD, by sub-stable emulsion after 30MPa homogeneous, be cooled to 30 ℃, obtain solid content and be in 20% stable both sexes potato starch AKD/alkaline sizing agent, described paraffin is semi-refined paraffin wax and fully refined paraffin wax mixture, both mass ratioes are 1: 2.
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| CN101759880A (en) * | 2010-01-13 | 2010-06-30 | 广东省造纸研究所 | Method for preparing amphiprotic starch solution for papermaking |
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| CN101759880A (en) * | 2010-01-13 | 2010-06-30 | 广东省造纸研究所 | Method for preparing amphiprotic starch solution for papermaking |
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Effective date of registration: 20201222 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. Effective date of registration: 20201222 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 |
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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: 20140611 |