CN101429742A - Surface sizing additive for papermaking - Google Patents
Surface sizing additive for papermaking Download PDFInfo
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- CN101429742A CN101429742A CNA2008101628760A CN200810162876A CN101429742A CN 101429742 A CN101429742 A CN 101429742A CN A2008101628760 A CNA2008101628760 A CN A2008101628760A CN 200810162876 A CN200810162876 A CN 200810162876A CN 101429742 A CN101429742 A CN 101429742A
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Abstract
The invention discloses a surface glue sizing auxiliary agent for paper making. The combination of the prior glue sizing auxiliary agent and fiber molecules mainly relies on actions of hydrogen bonds and ion bonds, and the glue sizing stability is poorer, and the glue sizing effect is easily affected by factors such as environmental temperature and humidity. The method for preparing the surface glue sizing auxiliary agent comprises the following steps: 1) hydrophobic monomers, hydrophilic monomers, solvent and initiator are mixed, added with functional auxiliary agent, and finally added with pH value regulating agent and water for stirring and diluting to obtain the semi-finished product of an emulsifying agent; and 2) the semi-finished product of the emulsifying agent, the pH value regulating agent, reduction initiator and water are mixed, and simultaneously added with the monomers and oxidation initiator to obtain the glue sizing auxiliary agent. The glue sizing auxiliary agent has the advantages of reacting with fiber to form a covalent bond, greatly shortening the curing time in the glue sizing process and obviously improving the water resistance and surface strength of the paper.
Description
Technical field
The present invention relates to paper making additive, specifically a kind of surface sizing additive for papermaking.
Background technology
In recent years, along with China's paper industry is already changed to modern paper by traditional paper-making industry, the industrial upgrading and the structural adjustment of domestic paper industry increasingly sharpen, and paper machine speed improves constantly, and the quality requirement of paper is strict more; Simultaneously, the use of non-wood pulps such as a large amount of careless oars, waste paper oar, the interpolation of various fillers causes the decline of page surface strength and smoothness, has aggravated phenomenon such as hair and powder dropping in the printing process.These have promoted the R and D of papermaking chemical products such as surface sizing additive greatly, particularly can improve the WATER RESISTANCE of paper surface and the paper making additive of picking strength fast.
Styrene-acrylic acid ester emulsion type sizing agent adopts water as polymerisation medium, meets current requirements of green environmental protection.In recent years, cinnamic acrylic ester emulsion glue sizing auxiliary agent is developed gradually.Chinese patent CN1323318A adopt polysaccharide and weight average molecular weight be 1000 or higher synthetic polymer (as polyvinyl alcohol, polyacrylamide etc.) as stabilizing agent, prepare the benzene emulsion sizing agent.Chinese patent CN1402805A as dispersant, makes the anion benzene emulsion by macromolecule or material with surface-activity ability in the presence of the alkali metal salt of shellac.Chinese patent CN1446233A then with the aqueous solution of starch or starch derivatives as emulsifying agent.Chinese patent CN1546792A adopts commercial nonionic or anionic small-molecular emulsifier, has made the good benzene emulsion of chemical stability.Chinese patent CN1749480A, CN1944792A and CN101148842A then mainly adopt the composite benzene emulsion for preparing of multiple anionic or cationic dispersing agent.Chinese patent CN10139808A then with behind shitosan and the functional monomer DMM reaction modifying, carries out emulsion polymerisation with N hydroxymethyl acrylamide and acrylate etc. again.
In above-mentioned patent, basically all partly or entirely choose small-molecular emulsifier, surfactant or water-soluble polymer etc. as disperseing or emulsifying agent, have certain hydrophily, sizing agent molecule and starch relatively slow in conjunction with speed, the curing time under the paper sizing behind the machine is longer; The combination of glue sizing auxiliary agent and fiber molecule mainly depends on the effect of hydrogen bond, ionic bond, the sizing efficiency less stable, and sizing efficiency is subject to factor affecting such as environment temperature, humidity.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, provide a kind of emulsifying agent that obtains by hydrophobic monomer and the reaction of functionalization auxiliary agent to prepare surface sizing additive, it has to react with fiber and constitutes the ability of covalent bond, to shorten the curing time of applying glue process greatly, obviously improve the WATER RESISTANCE and the surface strength of paper.
For this reason, the present invention adopts following technical scheme: surface sizing additive for papermaking, its preparation method are following steps:
1) hydrophobic monomer, hydrophilic monomer, solvent and initator are mixed, be warming up to 70-90 ℃, stirring reaction 1-5h then, adds the functionalization auxiliary agent, continues reaction 0.5-3h, adds pH value conditioning agent, water at last, and agitation and dilution gets the emulsifying agent semi-finished product;
In the reaction system, each component ratio of raw material is as follows:
(ratio between hydrophilic monomer and the hydrophobic monomer is monomer 16-20%
Between 4:1～1:3)
Molecular weight regulator 0-3%
Solvent 5-75%
Initator 0.1-3%
Functionalization auxiliary agent 0.5-8%
PH value conditioning agent 0.5-5%
Water 25-70%
Wherein, described hydrophobic monomer is styrene, α-Jia Jibenyixi, contains C
1-C
4Any one or two kinds of above mixtures in substituent styrene, methyl methacrylate, ethyl methacrylate, ethyl acrylate, n-BMA, n-butyl acrylate, metering system tert-butyl acrylate, the tert-butyl acrylate; Described hydrophilic monomer is any one or two kinds of above mixtures in acrylonitrile, acrylamide, Methacrylamide, acrolein, acrylic acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, acrylic acid dimethylamino ethyl ester, the methyl propenoic acid glycidyl ether.
Described molecular weight regulator is any or the mixture more than two kinds of normal-butyl mercaptan, lauryl mercaptan, tert-butyl mercaptan, uncle's lauryl mercaptan.
Described solvent is any or the mixture more than two kinds in water, isopropyl alcohol, methyl alcohol, ethanol, acetone, the butanone.
Described initator is any or the mixture more than two kinds in sodium peroxydisulfate, potassium peroxydisulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride, the azo diisopropylamidinateand azoles quinoline hydrochloride.
Described functionalization auxiliary agent be cationic starch, glyoxal, any one or two kinds of above mixtures in the glutaraldehyde, epoxychloropropane, pentaerythrite.
It is 35% aqueous sulfuric acid that described pH value conditioning agent is selected glacial acetic acid, concentrated hydrochloric acid or mass concentration for use.
The present invention adopts homemade cationic polymer as emulsifying agent, and it obtains by the reaction of amido macromolecule and functionalization auxiliary agent, and this emulsifying agent has to react with fiber and constitutes the ability of covalent bond, has also reduced its hydrophilicity.
2) the emulsifying agent semi-finished product that step 1) obtained mix with molecular weight regulator, pH value conditioning agent, reduction initator and water, are warming up to 50-80 ℃, drip monomer, oxidation initator simultaneously, then, are incubated to 75-95 ℃, and reaction 1-8h gets glue sizing auxiliary agent.
In the reaction system, each component ratio of raw material is as follows:
Emulsifying agent semi-finished product 10-60%
Monomer 10-30%
Molecular weight regulator 0-3%
PH value conditioning agent 0.5-5%
Oxidation, reduction initator 0.05-6%
Water 30-75%
Wherein, described monomer is styrene, α-Jia Jibenyixi, contains C
1-C
4In substituent styrene, methyl methacrylate, ethyl methacrylate, ethyl acrylate, n-BMA, n-butyl acrylate, metering system tert-butyl acrylate, tert-butyl acrylate, acrylonitrile, the acrolein any or the mixture more than two kinds.
Described molecular weight regulator is any or the mixture more than two kinds in normal-butyl mercaptan, lauryl mercaptan, tert-butyl mercaptan, the uncle's lauryl mercaptan.
It is 35% aqueous sulfuric acid that described pH value conditioning agent is selected glacial acetic acid, concentrated hydrochloric acid or mass concentration for use.
Described reduction initator is NaHSO
3, Na
2SO
3, FeCl
2, FeSO
4In any or the mixture more than two kinds; The oxidation initator is any or the mixture more than two kinds in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, azo-bis-isobutyrate hydrochloride, the azo diisopropylamidinateand azoles quinoline hydrochloride.
The half-finished solid content of emulsifying agent of the present invention is 15-30%, and the solid content of styrene-acrylic emulsion is 20-35%.
The present invention has the following advantages:
(1) the present invention adopts cationic polymeric compound that the reaction of amido macromolecule and functionalization auxiliary agent obtains as emulsifying agent, improved the binding ability between glue sizing auxiliary agent molecule and fiber, the size-press starch, accelerate the slaking speed and the sizing efficiency of paper sizing process, can satisfy the production requirement of high speed paper machine.
(2) surface sizing additive of the present invention is cationic styrene-acrylic microemulsion, can make the positive charge of trace on the paper surface band after the applying glue, has improved ink absorption, the printing performance of paper.
(3) surface sizing additive of the present invention mainly adopts water to do solvent and reaction medium, meets current requirements of green environmental protection.
(4) surface sizing additive of the present invention can be used for the surface treatment of paper such as white board, art post paperboard, corrugated paper and cultural paper.
The invention will be further described below in conjunction with the specific embodiment.
The specific embodiment
Embodiment 1
In the four-hole boiling flask that has condenser, Dropping feeder, agitator and thermometer, add 20g styrene, 10g butyl acrylate, 20g acrylonitrile, 30g dimethylaminoethyl methacrylate, 280g water, 20g ethanol, 0.5g lauryl mercaptan and 2g sodium peroxydisulfate.Stir, be warming up to 70 ℃, reaction 2h.Then, add the 8g glyoxal, reaction 1h.Then, add the 10g concentrated hydrochloric acid, continue to stir 10min, add water 40g, cooling discharging gets the emulsifying agent semi-finished product, and its solid content is 20%.
With 80g emulsifying agent semi-finished product, 5g concentrated hydrochloric acid, 0.5g ferrous sulfate and 160g water, join in the 500ml four-hole boiling flask that has condenser, agitator and thermometer.Stir, be warming up to 80 ℃, drip the mixture of 40g styrene and 52g metering system tert-butyl acrylate simultaneously, 20g5wt% sodium peroxydisulfate solution stirs 10min, and the dropping time is controlled at about 2.5h.Then, be warming up to 90 ℃, reaction 1.5h.Cooling discharging gets the surface sizing additive finished product, and its solid content is 30%.
Embodiment 2
In the 500ml four-hole boiling flask that has condenser, Dropping feeder, agitator and thermometer, add 20g methyl styrene, 40g acrylamide, 20g acrylic acid lignocaine ethyl ester, 10g acrolein, 80g acetone, 40g methyl alcohol, 1g butanethiol and 12g azodiisobutyronitrile.Stir, be warming up to 80 ℃, reaction 3h.Then, add the 2g pentaerythrite, reaction 0.5h.Then, add the 2g glacial acetic acid, continue to stir 10min, add water 75g, cooling discharging gets the emulsifying agent semi-finished product, and its solid content is 30%.
With 150g emulsifying agent semi-finished product, 10g concentrated hydrochloric acid, 0.5g sodium hydrogensulfite and 160g water, join in the four-hole boiling flask that has condenser, agitator and thermometer.Stir, be warming up to 70 ℃, drip monomer mixture (55g styrene, 15g butyl acrylate and 10g metering system tert-butyl acrylate), 10g hydrogen peroxide simultaneously, the dropping time is controlled at about 1.5h.Dropwise, be warming up to 75 ℃, insulation reaction 8h.Cooling discharging gets the surface sizing additive finished product, and its solid content is 30%.
Embodiment 3
With 15g α-Jia Jibenyixi, 5g acrylonitrile, 10g acrolein, 20g acrylic acid dimethylamino ethyl ester, 10g Methacrylamide, 20g isopropyl alcohol, 350g water and 5g azo diisopropylamidinateand azoles quinoline hydrochloride, join in the 1000ml four-hole boiling flask that has condenser, agitator and thermometer.Stir, be warming up to 90 ℃, reaction 1h.Then, add the 22g cationic starch, keep temperature-resistant, reaction 30min.Then, disposable adding 32g35% dilute sulfuric acid continues to stir 10min, adds 90g water again.Cooling discharging gets the emulsifying agent semi-finished product, and its solid content is 15%.
In the 500ml four-hole boiling flask that has condenser, Dropping feeder, agitator and thermometer, add 240g emulsifying agent semi-finished product, 5g 35% dilute sulfuric acid, 2g frerrous chloride and 140g water.Stir, be warming up to 50 ℃.Then, add the monomer mixture of 40g methyl styrene, 37g butyl acrylate and 20g acrylonitrile simultaneously, the 20g 5wt% azo diisopropylamidinateand azoles quinoline hydrochloride aqueous solution, the dropping time is controlled at about 1.5h.Then, be warming up to 80 ℃, reaction 3h.Cooling discharging gets the surface sizing additive finished product, and its solid content is 25%.
Embodiment 4
In the 500ml four-hole boiling flask that has condenser, Dropping feeder, agitator and thermometer, add 20g to ethyl styrene, 30g acrylonitrile, 30g dimethylaminoethyl methacrylate, 20g ethanol, 80g water, uncle's 0.5g lauryl mercaptan and 3g azodiisobutyronitrile.Stir, be warming up to 75 ℃, reaction 3h.Then, add the 8g epoxychloropropane, reaction 0.5h.Then, add 10g 35% dilute sulfuric acid rapidly, continue to stir 10min, add water 50g, cooling discharging gets the emulsifying agent semi-finished product, and its solid content is 35%.
With 80g emulsifying agent semi-finished product, 5g35% dilute sulfuric acid, 0.5g ferrous sulfate, 0.1g lauryl mercaptan and 150g water, join in the 500ml four-hole boiling flask that has condenser, agitator and thermometer.Stir, be warming up to 75 ℃, drip 40g styrene, 12g mixture simultaneously ethyl styrene and 40g ethyl methacrylate, 20g 5wt% azo-bis-isobutyrate hydrochloride solution, the dropping time is controlled at about 3h.Then, be warming up to 85 ℃, reaction 2h.Cooling discharging gets the surface sizing additive finished product, and its solid content is 35%.
Embodiment 5
In the 500ml four-hole boiling flask that has condenser, Dropping feeder, agitator and thermometer, add 30g styrene, 10g acrylic acid, 14g methyl propenoic acid glycidyl ether, 26g acrylic acid dimethylamino ethyl ester, 40g butanone, 60g ethanol, uncle's 0.5g lauryl mercaptan and 3g azodiisobutyronitrile.Stir, be warming up to 85 ℃, reaction 2h.Then, add the 8g glutaraldehyde, reaction 2h.Then, add the mixed solution of 10g glacial acetic acid and 40g water rapidly, continue to stir 10min, add water 200g, cooling discharging gets the emulsifying agent semi-finished product, and its solid content is 20%.
With 80g emulsifying agent semi-finished product, 5g concentrated hydrochloric acid, 0.5g NaHSO
3, 0.1g lauryl mercaptan and 210g water, join in the 500ml four-hole boiling flask that has condenser, agitator and thermometer.Stir, be warming up to 65 ℃, drip monomer mixture (60g styrene, 32g metering system tert-butyl acrylate), 20g 5wt% persulfate aqueous solution simultaneously, the dropping time is controlled at about 2.5h.Then, be warming up to 90 ℃, reaction 2.5h.Cooling discharging gets the surface sizing additive finished product, and its solid content is 25%.
The foregoing description 1-5 resulting styrene-acrylic emulsions, carry out following paper for surface sizing measure of merit:
1, adopt coated manila C level paperboard as body paper.
2, starch gelatinization: with mass percent concentration is the heating of 10% the oxidized starch aqueous solution, heats up 90 ℃, is incubated 10-20 minute.Thin up to 8% is incubated stand-by at 70 ℃.
3, surface sizing additive consumption: 0.3kg (over dry)/ton paper.
4, applying glue coating method: scraper type coating machine.
5, Cobb pH-value determination pH: the XSH type of employing Hangzhou Qingtong Boke Automation Technology Co., Ltd. is the absorbability analyzer suddenly, detects pattern to be measured by GB/T1540-1989 method.
6, become the physical index of paper:
The above only is preferred embodiment of the present invention, is not technical scheme of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all falls within the scope of protection of the present invention any simple modification, equivalent variations and modification that above embodiment did.
Claims (9)
1, a kind of surface sizing additive for papermaking, its preparation method is: 1) hydrophobic monomer, hydrophilic monomer, solvent and initator are mixed, be warming up to 70-90 ℃, stirring reaction 1-5h then, adds the functionalization auxiliary agent, continue reaction 0.5-3h, add pH value conditioning agent, water at last, agitation and dilution gets the emulsifying agent semi-finished product; 2) emulsifying agent semi-finished product, pH value conditioning agent, reduction initator and water are mixed, be warming up to 50-80 ℃, drip monomer, oxidation initator simultaneously, then, be incubated to 75-95 ℃, reaction 1-8h gets glue sizing auxiliary agent.
2, surface sizing additive for papermaking according to claim 1 is characterized in that the hydrophobic monomer described in the step 1) is styrene, α-Jia Jibenyixi, contains C
1-C
4Any one or two kinds of above mixtures in substituent styrene, methyl methacrylate, ethyl methacrylate, ethyl acrylate, n-BMA, n-butyl acrylate, metering system tert-butyl acrylate, the tert-butyl acrylate; Described hydrophilic monomer is any one or two kinds of above mixtures in acrylonitrile, acrylamide, Methacrylamide, acrolein, acrylic acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, acrylic acid dimethylamino ethyl ester, the methyl propenoic acid glycidyl ether.
3, surface sizing additive for papermaking according to claim 1 is characterized in that solvent in the step 1) is any one or two kinds of above mixtures in water, isopropyl alcohol, methyl alcohol, ethanol, acetone, the butanone.
4, surface sizing additive for papermaking according to claim 1 is characterized in that initator in the step 1) is any one or two kinds of above mixtures in sodium peroxydisulfate, potassium peroxydisulfate, azodiisobutyronitrile, azo-bis-isobutyrate hydrochloride, the azo diisopropylamidinateand azoles quinoline hydrochloride.
5, surface sizing additive for papermaking according to claim 1, it is characterized in that functionalization auxiliary agent in the step 1) be cationic starch, glyoxal, any one or two kinds of above mixtures in the glutaraldehyde, epoxychloropropane, pentaerythrite.
6, surface sizing additive for papermaking according to claim 1 is characterized in that step 2) in monomer be styrene, α-Jia Jibenyixi, contain C
1-C
4In substituent styrene, methyl methacrylate, ethyl methacrylate, ethyl acrylate, n-BMA, n-butyl acrylate, metering system tert-butyl acrylate, tert-butyl acrylate, acrylonitrile, the acrolein any or the mixture more than two kinds.
7, surface sizing additive for papermaking according to claim 1 is characterized in that step 2) in the reduction initator be NaHSO
3, Na
2SO
3, FeCl
2, FeSO
4In any or the mixture more than two kinds; The oxidation initator is any or the mixture more than two kinds in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, hydrogen peroxide, azo-bis-isobutyrate hydrochloride, the azo diisopropylamidinateand azoles quinoline hydrochloride.
8, surface sizing additive for papermaking according to claim 1, it is characterized in that step 1) and 2) reaction raw materials in all added molecular weight regulator, this molecular weight regulator is any one or two kinds of above mixtures in normal-butyl mercaptan, lauryl mercaptan, tert-butyl mercaptan, the uncle's lauryl mercaptan.
9,, it is characterized in that it is 35% aqueous sulfuric acid that described pH value conditioning agent is selected glacial acetic acid, concentrated hydrochloric acid or mass concentration for use according to claim 1 or 8 described surface sizing additive for papermaking.
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|---|---|---|---|
| CN2008101628760A CN101429742B (en) | 2008-12-08 | 2008-12-08 | Surface sizing additive for papermaking |
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| CN101429742B CN101429742B (en) | 2010-10-06 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885591A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化灌工程有限公司 | Polymer-type water glass curing agent and application in water glass chemical grouting materials |
| CN102675515A (en) * | 2011-12-16 | 2012-09-19 | 乐平市奇科化工有限公司 | Surface sizing agent and preparation method thereof |
| CN102767110A (en) * | 2011-05-05 | 2012-11-07 | 天津广聚源纸业有限公司 | Surface sizing method in corrugating medium production process |
| CN104403055A (en) * | 2014-11-11 | 2015-03-11 | 安徽综艺包装科技有限公司 | Styrene acrylic emulsion surface sizing agent and preparation method thereof |
| CN104829769A (en) * | 2015-05-11 | 2015-08-12 | 浙江理工大学 | Method for preparing cationic surface sizing agent employing environment-friendly solvent |
| CN105713131A (en) * | 2014-12-04 | 2016-06-29 | 上海东升新材料有限公司 | Styrene-acrylic emulsion, preparation method and application thereof |
| CN106188402A (en) * | 2016-06-30 | 2016-12-07 | 浙江弘利防渗胶有限公司 | A kind of waterborne epoxy modified acrylic emulsion and preparation method thereof |
| CN111424462A (en) * | 2020-04-01 | 2020-07-17 | 广东麦可瑞化工科技有限公司 | Water-resistant moisture-proof agent for paper and preparation method thereof |
| CN111888803A (en) * | 2020-06-30 | 2020-11-06 | 浙江传化华洋化工有限公司 | Oleate modified organic silicon defoaming agent for coating and preparation method thereof |
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2008
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885591A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化灌工程有限公司 | Polymer-type water glass curing agent and application in water glass chemical grouting materials |
| CN101885591B (en) * | 2010-07-12 | 2013-09-18 | 中科院广州化灌工程有限公司 | Polymer-type water glass curing agent and application in water glass chemical grouting materials |
| CN102767110A (en) * | 2011-05-05 | 2012-11-07 | 天津广聚源纸业有限公司 | Surface sizing method in corrugating medium production process |
| CN102675515A (en) * | 2011-12-16 | 2012-09-19 | 乐平市奇科化工有限公司 | Surface sizing agent and preparation method thereof |
| CN104403055A (en) * | 2014-11-11 | 2015-03-11 | 安徽综艺包装科技有限公司 | Styrene acrylic emulsion surface sizing agent and preparation method thereof |
| CN105713131A (en) * | 2014-12-04 | 2016-06-29 | 上海东升新材料有限公司 | Styrene-acrylic emulsion, preparation method and application thereof |
| CN104829769A (en) * | 2015-05-11 | 2015-08-12 | 浙江理工大学 | Method for preparing cationic surface sizing agent employing environment-friendly solvent |
| CN104829769B (en) * | 2015-05-11 | 2017-06-16 | 浙江理工大学 | A kind of method that environmentally friendly solvent prepares cation surface sizing agent |
| CN106188402A (en) * | 2016-06-30 | 2016-12-07 | 浙江弘利防渗胶有限公司 | A kind of waterborne epoxy modified acrylic emulsion and preparation method thereof |
| CN111424462A (en) * | 2020-04-01 | 2020-07-17 | 广东麦可瑞化工科技有限公司 | Water-resistant moisture-proof agent for paper and preparation method thereof |
| CN111888803A (en) * | 2020-06-30 | 2020-11-06 | 浙江传化华洋化工有限公司 | Oleate modified organic silicon defoaming agent for coating and preparation method thereof |
| CN111888803B (en) * | 2020-06-30 | 2021-10-29 | 浙江传化华洋化工有限公司 | Oleate modified organic silicon defoaming agent for coating and preparation method thereof |
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