CN102627730A - Amphoteric dry strength agent and preparation method thereof - Google Patents
Amphoteric dry strength agent and preparation method thereof Download PDFInfo
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- CN102627730A CN102627730A CN2012100883848A CN201210088384A CN102627730A CN 102627730 A CN102627730 A CN 102627730A CN 2012100883848 A CN2012100883848 A CN 2012100883848A CN 201210088384 A CN201210088384 A CN 201210088384A CN 102627730 A CN102627730 A CN 102627730A
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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
The Along with people's growth in the living standard; Demand and consumption to paper constantly increase; 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 especially careless type of paper, waste paper and other short fiber material papermaking is that ten minutes is necessary.
Domestic paper making intensifier commonly used mainly is treated starch, polyacrylamide toughener at present; But starch and verivate thereof have advantages such as aboundresources, the biological degradation of low price chemical modifier; But compare with starch, SEPIGEL 305 has the advantage that just can obtain good reinforced effects with addition seldom again.The exploitation of SEPIGEL 305 at present drops into more in amphoteric type, has formed than big market.This is to be fit to different paper technologies because both sexes gather propionic acid amide.Most of amphiprotic polyacrylamide turns to purpose with high density and HMW and brings the ramiform structure into, can strengthen the absorption to paper pulp, increases paper strength.But starch based toughener addition is big, is prone to the mould degraded that becomes different for a long time; When SEPIGEL 305 used separately, it was not obvious to improve deflection and ring crush intensity.
Summary of the invention
The purpose of this invention is to provide a kind of both sexes Dry Strength Resin and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) in nitrogen atmosphere, the pH value is under the condition of 9-10, and etherifying agent and oxygenant are added milk of starch, and 40-60 ℃ was reacted 1-2 hour;
Wherein, the pH value can be regulated said alkaline matter such as sodium hydroxide, Pottasium Hydroxide or ammoniacal liquor through adding alkaline matter;
Described etherifying agent is a kind of in 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 3-chloro-2-hydroxyethyl trimethyl ammonium chloride or the 3-chloro-2-hydroxypropyl triethyl ammonium chloride, and it is the 3-5% of starch that etherifying agent adds weight;
Described oxygenant is Youxiaolin, potassium permanganate or ydrogen peroxide 50, preferred ydrogen peroxide 50, 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 the yam starch;
(2) add vinyl cyanide then, 90-95 ℃ was reacted 1-2 hour, and the pH value that adds the acidic substance regulation system is to 7-8;
It is 1～2% of starch that vinyl cyanide adds weight;
Said acidic substance comprise hydrochloric acid, phosphoric acid, nitric acid or sulfuric acid;
(3) add acrylic amide, cationic monomer and initiator, room temperature is reduced in reaction 2-4 hour, crosses 100 order nets, and discharging can obtain described both sexes biotype Dry Strength Resin;
Described cationic monomer is a kind of in methylacryoyloxyethyl trimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac or the acrylonitrile-chlorinated ammonium of dimethyl-diene, and the adding weight of cationic monomer is 8～10% of starch;
It is 45～75% of starch that acrylic amide adds weight;
Said initiator is a kind of in ammonium persulphate, Sodium Persulfate or the Potassium Persulphate, and it adds weight is the 1.0-6.0% of cationic monomer.
The present invention adopts cationic starch cyanoethylation grafting cationic polyacrylamide, makes the zwitterionic paper dry strength agent with excellent effect.Be used for dry strength agent in the paper slurry; Owing to self have a large amount of positive charge; The cationic of self is adsorbed on the fiber surface, so when trace adds in the slurry, need not to add any retention aid; And avoided the defective of starch and polyacrylamide dry strength agent, the each item that can significantly improve paper is done strong index.
Embodiment
Among the embodiment, if no special instructions, the consumption of component is weight part.
Embodiment 1
(1) etherification reaction: in the four-hole boiling flask that stirring, TM, breather line and dropping pipeline are housed, add 314 parts of deionized waters, open and stir, logical nitrogen; Under agitation add 40 parts of W-Gums; Heat temperature raising to 40 ℃ stirred after 30 minutes, added 1.7 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 0.4 part in the ydrogen peroxide 50 of effective weight content 69%; With the pH value to 9.0 of sodium hydroxide accent solution, and under this temperature, reacted 2 hours;
(2) cyanogenation: add 0.4 part of vinyl cyanide, system is warming up to 90 ℃, forms dextrin, and reaction is 2 hours under this temperature, and the pH value to 7.0 with hydrochloric acid is transferred solution gets translucent yellow solution;
(3) graft reaction: add 30 parts of acrylic amides and weight concentration in the system and be 14 parts of 69% cationic monomer methylacryoyloxyethyl trimethyl ammonium chlorides; After stirring, add 0.9 part of initiator ammonium persulfate, 80 ℃ of reactions after 3 hours; Reduce to room temperature; Cross 100 order nets, both getting the weight solid content is 20.5%, and viscosity is the both sexes Dry Strength Resin of 40cps.
Embodiment 2
(1) etherification reaction: in the four-hole boiling flask that stirring, TM, breather line and dropping pipeline are housed, add 312 parts of deionized waters, open and stir, logical nitrogen; Under agitation add 48 parts of wheat starches; Heat temperature raising to 60 ℃ stirred after 20 minutes, added 2.8 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 1.0 parts in the ydrogen peroxide 50 of effective weight content 69%; With the pH value to 9.5 of sodium hydroxide accent solution, and under this temperature, reacted 1.0 hours;
(2) cyanogenation: add 0.7 part of vinyl cyanide, system is warming up to 90 ℃, forms dextrin, and reaction is 1.5 hours under this temperature, and the pH value to 7.5 with hydrochloric acid is transferred solution gets translucent yellow solution;
(3) graft reaction: add 24 parts of acrylic amides and weight concentration in the system and be 11 parts of 60% cationic monomer acrylyl oxy-ethyl-trimethyl salmiacs; After stirring, add 0.3 part of initiator ammonium persulfate, 85 ℃ of reactions after 4 hours; Reduce to room temperature; Cross 100 order nets, both getting the weight solid content is 20.0%, and viscosity is the both sexes Dry Strength Resin of 60cps.
Embodiment 3
(1) etherification reaction: in the four-hole boiling flask that stirring, TM, breather line and dropping pipeline are housed, add 309 parts of deionized waters, open and stir, logical nitrogen; Under agitation add 55 parts of tapioca(flour)s; Heat temperature raising to 60 ℃ stirred after 10 minutes, added 4.0 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 1.7 parts in the ydrogen peroxide 50 of effective weight content 69%; With the pH value to 10.0 of sodium hydroxide accent solution, and under this temperature, reacted 1.0 hours;
(2) cyanogenation: add 1.1 parts of vinyl cyanide, system is warming up to 95 ℃, forms dextrin, and reaction is 2 hours under this temperature, and the pH value to 8.0 with hydrochloric acid is transferred solution gets translucent yellow solution;
(3) graft reaction: add 26 parts of acrylic amides and weight concentration in the system and be 15 parts of 60% cationic monomer diallyldimethylammonChloride Chlorides; After stirring, add 1.8 parts of initiator ammonium persulfates, 85 ℃ of reactions after 2 hours; Reduce to room temperature; Cross 100 order nets, both getting the weight solid content is 25.1%, and viscosity is the both sexes Dry Strength Resin of 90cps.
Embodiment 4
(1) etherification reaction: in the four-hole boiling flask that stirring, TM, breather line and dropping pipeline are housed, add 310 parts of deionized waters, open and stir, logical nitrogen; Under agitation add 52 parts of yam starchs; Heat temperature raising to 55 ℃ stirred after 30 minutes, added 3.4 parts of 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, 1.3 parts in the ydrogen peroxide 50 of effective weight content 69%; With the pH value to 9.8 of sodium hydroxide accent solution, and under this temperature, reacted 1.5 hours;
(2) cyanogenation: add 0.8 part of vinyl cyanide, system is warming up to 92 ℃, forms dextrin, and reaction is 1.5 hours under this temperature, and the pH value to 7.3 with hydrochloric acid is transferred solution gets translucent yellow solution;
(3) graft reaction: add 35 parts of acrylic amides and weight concentration in the system and be 17 parts of 60% cationic monomer methylacryoyloxyethyl trimethyl ammonium chlorides; After stirring, add 2.7 parts of initiator ammonium persulfates, 82 ℃ of reactions after 3.5 hours; Reduce to room temperature; Cross 100 order nets, both getting the weight solid content is 24.8%, and viscosity is the both sexes Dry Strength Resin of 87cps.
Embodiment 5
Design the quantitative 125g/m that manufactures paper with pulp
2About, order of addition(of ingredients) is: slurry+Tai-Ace S 150+Dry Strength Resin, Tai-Ace S 150 are added in earlier in the underflow, and dosage is 42 kilograms (liquid)/ton paper (liquid aluminium sulfate, it is 38% that 150 ℃ of bakings got solid content in 30 minutes), stirs 10 minutes.Dry Strength Resin is under the situation of same addition, and this invents the application result of product and comparative sample.Take by weighing the slurry of an amount of adding Tai-Ace S 150; Adding Dry Strength Resin then stirred 2 minutes; After the square handshcet former was copied sheet and squeezing, natural air drying detected the indexs such as tensile strength (GB/T 12914-1991), ring crush intensity (GB/T 2678.8-1995), folding endurance of paper then.
Annotate: comparison sample is the product of patent CN101597875 method preparation, can find out that from table its tensile index, ring crush index and folding number are compared with comparative sample, all are improved to some extent.
Claims (10)
1. the preparation method of both sexes Dry Strength Resin is characterized in that, comprises the steps:
(1) in nitrogen atmosphere, etherifying agent and oxygenant are added milk of starch, reaction;
(2) add vinyl cyanide then, reaction, the pH value that adds the acidic substance regulation system is to 7-8;
(3) add acrylic amide, cationic monomer and initiator, room temperature is reduced in reaction, crosses net, and discharging can obtain described both sexes biotype Dry Strength Resin.
2. method according to claim 1 is characterized in that, in nitrogen atmosphere, the pH value is under the condition of 9-10, and etherifying agent and oxygenant are added milk of starch, and 40-60 ℃ was reacted 1-2 hour.
3. method according to claim 1; It is characterized in that; Described etherifying agent is a kind of in 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, 3-chloro-2-hydroxyethyl trimethyl ammonium chloride or the 3-chloro-2-hydroxypropyl triethyl ammonium chloride, and it is the 3-5% of starch that etherifying agent adds weight;
Described oxygenant is Youxiaolin, potassium permanganate or ydrogen peroxide 50.
4. method according to claim 3 is characterized in that, described starch is a kind of in wheat starch, W-Gum, tapioca(flour) and the yam starch.
5. method according to claim 1 is characterized in that, in the step (2), adds vinyl cyanide, and 90-95 ℃ was reacted 1-2 hour.
6. method according to claim 5 is characterized in that, it is 1～2% of starch that vinyl cyanide adds weight.
7. method according to claim 5 is characterized in that said acidic substance comprise hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid.
8. method according to claim 1 is characterized in that, in the step (3), adds acrylic amide, cationic monomer and initiator, reaction 2-4 hour.
9. method according to claim 8; It is characterized in that; Described cationic monomer is a kind of in methylacryoyloxyethyl trimethyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac or the acrylonitrile-chlorinated ammonium of dimethyl-diene, and the adding weight of cationic monomer is 8～10% of starch;
It is 45～75% of starch that acrylic amide adds weight;
Said initiator is a kind of in ammonium persulphate, Sodium Persulfate or the Potassium Persulphate, and it adds weight is the 1.0-6.0% of cationic monomer.
10. the both sexes Dry Strength Resin for preparing according to each described method of claim 1～9.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408702A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Preparation method of graft-polymer cationic dry strength agent |
| CN103435752A (en) * | 2013-07-09 | 2013-12-11 | 上海东升新材料有限公司 | Synthesis method for graft polymer-type amphoteric dry strength agent |
| CN105111378A (en) * | 2015-09-29 | 2015-12-02 | 赵迎辉 | Cationic polymer grafting modified nanocrystalline cellulose and preparation method and application thereof |
| 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 |
| CN105786052A (en) * | 2014-12-16 | 2016-07-20 | 艺康美国股份有限公司 | Online control and reaction method for pH regulation |
| CN106283873A (en) * | 2016-08-25 | 2017-01-04 | 董晓 | A kind of preparation method of potato starch 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 |
| CN110407974A (en) * | 2019-08-15 | 2019-11-05 | 浙江传化华洋化工有限公司 | A kind of preparation method of cross-linking amphiprotic 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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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408702A (en) * | 2013-07-09 | 2013-11-27 | 上海东升新材料有限公司 | Preparation method of graft-polymer cationic dry strength agent |
| CN103435752A (en) * | 2013-07-09 | 2013-12-11 | 上海东升新材料有限公司 | Synthesis method for graft polymer-type amphoteric 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 |
| CN105786052A (en) * | 2014-12-16 | 2016-07-20 | 艺康美国股份有限公司 | Online control and reaction method for pH regulation |
| 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 |
| CN105111378A (en) * | 2015-09-29 | 2015-12-02 | 赵迎辉 | Cationic polymer grafting modified nanocrystalline cellulose and preparation method and application thereof |
| CN106283873A (en) * | 2016-08-25 | 2017-01-04 | 董晓 | A kind of preparation method of potato starch 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 |
| CN110407974A (en) * | 2019-08-15 | 2019-11-05 | 浙江传化华洋化工有限公司 | A kind of preparation method of cross-linking amphiprotic 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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| CN102627730B (en) | 2014-01-29 |
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