CN102627730B - Amphoteric dry strength agent and preparation method thereof - Google Patents
Amphoteric dry strength agent and preparation method thereof Download PDFInfo
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- CN102627730B CN102627730B CN201210088384.8A CN201210088384A CN102627730B CN 102627730 B CN102627730 B CN 102627730B CN 201210088384 A CN201210088384 A CN 201210088384A CN 102627730 B CN102627730 B CN 102627730B
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Abstract
The invention discloses an amphoteric dry strength agent and a preparation method thereof. The preparation method comprises the following steps: firstly, adding an etherifying agent and an oxidizing agent into starch milk for reacting in the atmosphere of nitrogen gas; secondly, adding acrylonitrile in the mixture for reacting, adding an acidic material and adjusting the pH value of the system to 7-8; and thirdly, adding acrylamide, a cation monomer and an initiator and reacting, reducing the temperature to room temperature, sieving and discharging to obtain the amphoteric biological dry strength agent. According to the amphoteric dry strength agent disclosed by the invention, a large amount of positive charges exist in the amphoteric dry strength agent and cationoid of the amphoteric dry strength agent is adsorbed on the surface of fiber, so that trace amount of the amphoteric dry strength agent is added in the pulp is realized, no retention aid is required; in addition, the defects of starch and polyacrylamide dry strength agents are avoided and various dry strength indexes of paper can be remarkably improved.
Description
Technical field
The present invention relates to a kind of both sexes Dry Strength Resin and preparation method thereof.
Technical background
Raising along with people's living standard, the demand of paper and consumption are constantly increased, but China's Forest Resources is not enough, the papermaking of a large amount of dependence wood fiber raw material, the toughener of therefore developing the efficient and cheap that is applicable to the especially careless class of paper, waste paper and other short fiber material papermaking is very necessary.
Domestic conventional paper making intensifier is mainly treated starch, polyacrylamide toughener at present, starch and derivative thereof have aboundresources, low price, can chemical modifier biological degradation etc. advantage, but compare with starch, polyacrylamide has again with addition seldom just can obtain the advantage of good reinforced effects.The exploitation of polyacrylamide at present drops into more in amphoteric type, has formed larger market.This is because the poly-propionic acid amide of both sexes is applicable to different paper technologies.Most of amphiprotic polyacrylamide turns to object with high density and high molecular and brings ramiform structure into, can strengthen the absorption to paper pulp, increases paper strength.But starch based toughener addition is large, the long-time easily mould degraded that becomes different; When polyacrylamide is used separately, improve stiffness and ring crush compression resistance not obvious.
Summary of the invention
The object of this invention is to provide a kind of both sexes Dry Strength Resin and preparation method thereof, the above-mentioned defect existing to overcome prior art.
Method of the present invention, comprises the steps:
(1) in nitrogen atmosphere, under the condition that pH value is 9-10, etherifying agent and oxygenant are added to starch milk, 40-60 ℃ is reacted 1-2 hour;
Wherein, pH value, can be by adding alkaline matter to regulate, and described alkaline matter is as sodium hydroxide, potassium hydroxide or ammoniacal liquor;
Described etherifying agent is a kind of in 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, the chloro-choline chloride of 3-or the chloro-2-hydroxypropyl of 3-triethyl ammonium chloride, and it is the 3-5% of starch that etherifying agent adds weight;
Described oxygenant is clorox, potassium permanganate or hydrogen peroxide, preferred hydrogen peroxide, and adding weight is the 2.0-3.0% of starch;
Described starch is a kind of in wheat starch, W-Gum, tapioca (flour) and yam starch;
(2) then add vinyl cyanide, 90-95 ℃ is reacted 1-2 hour, adds the pH value of acidic substance regulation system to 7-8;
It is 1～2% of starch that vinyl cyanide adds weight;
Described acidic substance comprise hydrochloric acid, phosphoric acid, nitric acid or sulfuric acid;
(3) add acrylamide, cationic monomer and initiator, reaction 2-4 hour, is down to room temperature, crosses 100 order nets, and discharging, can obtain described both sexes biotype Dry Strength Resin;
Described cationic monomer is a kind of in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac or the acrylonitrile-chlorinated ammonium of dimethyl diene, and the weight that adds of cationic monomer is 8～10% of starch;
It is 45～75% of starch that acrylamide adds weight;
Described initiator is a kind of in ammonium persulphate, Sodium Persulfate or Potassium Persulphate, and it adds weight is the 1.0-6.0% of cationic monomer.
The present invention adopts cationic starch cyanoethylation grafted cation polyacrylamide, makes the zwitterionic paper dry strengthening agent with excellent effect.For dry strength agent in paper slurry, because self is with a large amount of positive charge, the cationic of self is adsorbed on fiber surface, so in slurry during indium addition, without adding any retention aid, and avoided the defect of starch and polyacrylamide dry strength agent, can significantly improve the every dry strong index of paper.
Embodiment
In embodiment, if no special instructions, the consumption of component is weight part.
Embodiment 1
(1) etherification reaction: add 314 parts of deionized waters in the four-hole boiling flask that stirring, thermometer, breather line and dropwise adding pipeline are housed, open and stir, logical nitrogen, under agitation add 40 parts of W-Gums, be heated to 40 ℃, stir after 30 minutes, add 1.7 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 0.4 part, the hydrogen peroxide of effective weight content 69%, with sodium hydroxide, adjust the pH value to 9.0 of solution, and react 2 hours at this temperature;
(2) cyanogenation: add 0.4 part of vinyl cyanide, system is warming up to 90 ℃, forms dextrin, at this temperature, reacts 2 hours, adjusts the pH value to 7.0 of solution with hydrochloric acid, obtains translucent yellow solution;
(3) graft reaction: add 14 parts of the cationic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides that 30 parts of acrylamides and weight concentration are 69% in system, after stirring, add 0.9 part of initiator ammonium persulfate, at 80 ℃, react after 3 hours, be down to room temperature, cross 100 order nets, both obtaining weight solid content is 20.5%, the both sexes Dry Strength Resin that viscosity is 40cps.
Embodiment 2
(1) etherification reaction: add 312 parts of deionized waters in the four-hole boiling flask that stirring, thermometer, breather line and dropwise adding pipeline are housed, open and stir, logical nitrogen, under agitation add 48 parts of wheat starches, be heated to 60 ℃, stir after 20 minutes, add 2.8 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 1.0 parts, the hydrogen peroxide of effective weight content 69%, with sodium hydroxide, adjust the pH value to 9.5 of solution, and react 1.0 hours at this temperature;
(2) cyanogenation: add 0.7 part of vinyl cyanide, system is warming up to 90 ℃, forms dextrin, at this temperature, reacts 1.5 hours, adjusts the pH value to 7.5 of solution with hydrochloric acid, obtains translucent yellow solution;
(3) graft reaction: add 11 parts of the cationic monomer acrylyl oxy-ethyl-trimethyl salmiacs that 24 parts of acrylamides and weight concentration are 60% in system, after stirring, add 0.3 part of initiator ammonium persulfate, at 85 ℃, react after 4 hours, be down to room temperature, cross 100 order nets, both obtaining weight solid content is 20.0%, the both sexes Dry Strength Resin that viscosity is 60cps.
Embodiment 3
(1) etherification reaction: add 309 parts of deionized waters in the four-hole boiling flask that stirring, thermometer, breather line and dropwise adding pipeline are housed, open and stir, logical nitrogen, under agitation add 55 parts of tapioca (flour)s, be heated to 60 ℃, stir after 10 minutes, add 4.0 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 1.7 parts, the hydrogen peroxide of effective weight content 69%, with sodium hydroxide, adjust the pH value to 10.0 of solution, and react 1.0 hours at this temperature;
(2) cyanogenation: add 1.1 parts of vinyl cyanide, system is warming up to 95 ℃, forms dextrin, at this temperature, reacts 2 hours, adjusts the pH value to 8.0 of solution with hydrochloric acid, obtains translucent yellow solution;
(3) graft reaction: add 15 parts of the cationic monomer diallyldimethylammonChloride Chlorides that 26 parts of acrylamides and weight concentration are 60% in system, after stirring, add 1.8 parts of initiator ammonium persulfates, at 85 ℃, react after 2 hours, be down to room temperature, cross 100 order nets, both obtaining weight solid content is 25.1%, the both sexes Dry Strength Resin that viscosity is 90cps.
Embodiment 4
(1) etherification reaction: add 310 parts of deionized waters in the four-hole boiling flask that stirring, thermometer, breather line and dropwise adding pipeline are housed, open and stir, logical nitrogen, under agitation add 52 parts of yam starchs, be heated to 55 ℃, stir after 30 minutes, add 3.4 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 1.3 parts, the hydrogen peroxide of effective weight content 69%, with sodium hydroxide, adjust the pH value to 9.8 of solution, and react 1.5 hours at this temperature;
(2) cyanogenation: add 0.8 part of vinyl cyanide, system is warming up to 92 ℃, forms dextrin, at this temperature, reacts 1.5 hours, adjusts the pH value to 7.3 of solution with hydrochloric acid, obtains translucent yellow solution;
(3) graft reaction: add 17 parts of the cationic monomer MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides that 35 parts of acrylamides and weight concentration are 60% in system, after stirring, add 2.7 parts of initiator ammonium persulfates, at 82 ℃, react after 3.5 hours, be down to room temperature, cross 100 order nets, both obtaining weight solid content is 24.8%, the both sexes Dry Strength Resin that viscosity is 87cps.
Embodiment 5
Design the quantitative 125g/m that manufactures paper with pulp
2left and right, order of addition(of ingredients) is: slurry+Tai-Ace S 150+Dry Strength Resin, Tai-Ace S 150 is first added in underflow, and dosage is 42 kilograms (liquid)/ton paper (liquid aluminium sulfate, 150 ℃ are dried 30 minutes to such an extent that solid content is 38%), stirs 10 minutes.Dry Strength Resin the in the situation that of same addition, the application result of this invention product and comparative sample.Take the slurry that adds in right amount Tai-Ace S 150, then add Dry Strength Resin to stir 2 minutes, after square handshcet former handsheet squeezing, natural air drying, then detects the indexs such as tensile strength (GB/T 12914-1991), ring crush intensity (GB/T 2678.8-1995), folding endurance of paper.
Note: contrast sample is product prepared by patent CN101597875 method, and as can be seen from the table, its tensile index, ring crush index and folding number are compared with comparative sample, are all improved to some extent.
Claims (6)
1. the preparation method of both sexes Dry Strength Resin, is characterized in that, comprises the steps:
(1) in nitrogen atmosphere, under the condition that pH value is 9-10, etherifying agent and oxygenant are added to starch milk, 40-60 ℃ is reacted 1-2 hour;
(2) then add vinyl cyanide, 90-95 ℃ is reacted 1-2 hour, adds the pH value of acidic substance regulation system to 7-8, and it is the 1-2% of starch that vinyl cyanide adds weight;
(3) add acrylamide, cationic monomer and initiator, reaction 2-4 hour, is down to room temperature, crosses net, and discharging, can obtain described both sexes Dry Strength Resin;
Described etherifying agent is a kind of in the chloro-choline chloride of 3-or the chloro-2-hydroxypropyl of 3-triethyl ammonium chloride, and it is the 3-5% of starch that etherifying agent adds weight;
Described cationic monomer is a kind of in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, and the weight that adds of cationic monomer is 8～10% of starch;
It is the 45-75% of starch that acrylamide adds weight;
It is the 1.0-6.0% of cationic monomer that described initiator adds weight.
2. method according to claim 1, is characterized in that, described oxygenant is clorox, potassium permanganate or hydrogen peroxide.
3. method according to claim 2, is characterized in that, described starch is a kind of in wheat starch, W-Gum, tapioca (flour) and yam starch.
4. method according to claim 1, is characterized in that, described acidic substance comprise hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid.
5. method according to claim 1, is characterized in that, described initiator is a kind of in ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
6. the both sexes Dry Strength Resin of preparing according to the method described in claim 1～5 any one.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435752B (en) * | 2013-07-09 | 2017-10-10 | 上海东升新材料有限公司 | The method for synthesizing graft-polymer both sexes drying strengthening agent |
| CN103408702B (en) * | 2013-07-09 | 2017-04-19 | 上海东升新材料有限公司 | Preparation method of graft-polymer cationic dry strength agent |
| CN105586805A (en) * | 2014-10-20 | 2016-05-18 | 东升新材料（山东）有限公司 | Paper fold-resistance reinforcing agent and preparation method thereof |
| CN105786052B (en) * | 2014-12-16 | 2020-09-08 | 艺康美国股份有限公司 | Online control and reaction method for pH adjustment |
| CN105111378B (en) * | 2015-09-29 | 2018-01-09 | 赵迎辉 | A kind of cationic polymer Grafted Nano-scale avicel cellulose and its preparation method and application |
| CN106283873B (en) * | 2016-08-25 | 2017-12-01 | 重庆益新阳工贸有限公司 | A kind of preparation method of farina biology drying strengthening agent |
| CN108060609A (en) * | 2017-12-07 | 2018-05-22 | 常州帝君金属构件厂 | A kind of preparation method of the compound drying strengthening agent of high bond strength |
| CN109653025A (en) * | 2018-12-12 | 2019-04-19 | 济宁明升新材料有限公司 | A kind of preparation method of natural polysaccharide and its derivative modified wet strengthening agents for papermaking |
| CN110407974B (en) * | 2019-08-15 | 2021-09-21 | 浙江传化华洋化工有限公司 | Preparation method of crosslinkable amphoteric polyacrylamide polymer |
| CN113171002A (en) * | 2021-04-26 | 2021-07-27 | 杭州西红柿环保科技有限公司 | Full-degradable paper pulp non-softening cup |
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