CN104988796A - Enhanced multifunctional surface sizing assistant for papermaking and preparation method thereof - Google Patents
Enhanced multifunctional surface sizing assistant for papermaking and preparation method thereof Download PDFInfo
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- CN104988796A CN104988796A CN201510289090.5A CN201510289090A CN104988796A CN 104988796 A CN104988796 A CN 104988796A CN 201510289090 A CN201510289090 A CN 201510289090A CN 104988796 A CN104988796 A CN 104988796A
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Abstract
The invention discloses a production formula of an enhanced multifunctional surface sizing assistant for papermaking and a preparation process. Specifically, the production formula involves: 5-15 parts of starch, 15-25 parts of a hydrophobic monomer, 2-15 parts of a hydrophilic monomer, 0-0.5 part of a crosslinking monomer, 0.1-5 parts of an initiator, 0.2-2 parts of glyoxal, 0-5 parts of a pH regulator, and the balance water. The sizing assistant prepared by the preparation process provided by the invention can enhance the strength indexes of paper and paper boards (like enhancing ring crush strength, bursting strength, folding endurance, moisture resistance and the like), also can endow paper and paper boards with good water resistance, meet the multipurpose sizing demands of paper and paper boards, and have good market prospects.
Description
Technical field
Paper grade (stock) multifunction surface glue sizing auxiliary agent that the present invention relates to a kind of enhancement mode and preparation method thereof, belongs to papermaking chemical product technical field.
Background technology
Carrying out top sizing to paper and paperboard is a kind of technique comparatively general in current paper industry and technology, can improve the surface property of paper, as: to improve in the WATER RESISTANCE of paper surface and smoothness, minimizing printing process the phenomenons such as hair and powder dropping.In the market, the type of Cypres is many, as AKD class emulsion, polyurethane aqueous dispersion (polyurethane dispersions, be called for short PUD class), the styrene one maleic anhydride polymer aqueous solution (Styrene maleic anhydride, be called for short SMA), styrene one aqueous acrylic polymer solution (styrene acrylic acids, be called for short SAA) and copolymer in cinnamic acrylic ester aqueous dispersions (Styreneacrylic emulsions is called for short SAE class) etc.Wherein, cinnamic acrylic ester class Cypres is the more a kind of synthetic surface sizing agent of current application and research,
Patent CN1446233A and CN101225623 hands over the polymer dispersed system of colloid using starch or starch derivatives as protection, have the features such as mechanical/chemical good stability, filtration residue are few.Patent CN1749480A, CN1944792A and CN101148842A then mainly adopt multiple anionic or the composite of cationic dispersing agent to prepare benzene emulsion.CN101139808A then by after shitosan and functional monomer DMM reaction modifying, then carries out emulsion polymerisation with N hydroxymethyl acrylamide and acrylate etc.
Surface sizing additive product in above-mentioned patent, mainly improves the surface smoothness of paper, water repelling property and printing performance etc., but relates to less to the target improvement such as ring crush intensity, burst index, folding strength of paper and paper.In actual production, although WATER RESISTANCE is good, the fireballing product of slaking is more, improve the product of the index such as ring crush intensity, folding strength, actually rare, urgently develop.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide the surface sizing additive of a kind of good stability, the ring crush intensity that effectively can improve paper or paper, burst index, folding strength, anti-moisture resistance and water repelling property, also disclose the preparation method of this surface sizing additive simultaneously.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
A paper grade (stock) multifunction surface glue sizing auxiliary agent for enhancement mode, comprises following component and the weight portion of each component is as follows:
Particularly, aforementioned starch is cassava modified starch, and before use through ammonium persulfate or catalyzed by amylase degraded.
Preferably, aforesaid hydrophobic monomer is for containing C
1-C
4the mixture of any one or more in substituent styrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, vinyl silane triisopropoxide, methyl allyl acyloxypropyl trimethoxysilane, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Tert-butyl Methacrylate and EHMA.Wherein, containing C
1-C
4substituent styrene includes but not limited to: styrene and α-methyl styrene.
Preferably, aforesaid hydrophilic monomer is the mixture of any one or more in acrylamide, Methacrylamide, acrylonitrile, acrolein, acrylic acid, maleic anhydride, fumaric acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, acrylate, acryloyloxyethyl trimethyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, acryloyl-oxyethyl dimethyl benzyl ammonium chloride and methacryloxyethyl dimethyl benzyl ammonium chloride.
More preferably, aforesaid cross-linking monomer is the mixture of any one or more in divinylbenzene, diallylamine and glycidyl methacrylate.
Particularly, aforesaid initator is the mixture of any one or more in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, persulphate-bisulphite sodium, hydrogen peroxide, hydrogen peroxide-ferrous sulfate, hydrogen peroxide-rongalite, azo-bis-isobutyrate hydrochloride or azo diisopropylamidinateand azoles quinoline hydrochloride.
Aforementioned pH adjusting agent is one or more in formic acid, glacial acetic acid, oxalic acid and aqueous sulfuric acid.
This surface sizing additive is a kind of nanoscale emulsion polymer, and solid content is 30-40%, and vitrification point is greater than 30 DEG C.
In addition, the invention also discloses the preparation method of the paper grade (stock) multifunction surface glue sizing auxiliary agent of foregoing a kind of enhancement mode, comprise the steps:
S1, prepare each raw material according to aforesaid parts by mass, be mixed in reaction vessel, be warming up to 80-95 DEG C by starch, glyoxal and water, insulation 5-30 minute, hierarchy of control viscosity is not higher than 25mPas;
S2, in reaction vessel, add pH adjusting agent and part initiator;
S3, maintain the temperature at 70-95 DEG C, simultaneously or substep drip monomer mixed solution, initiator solution, dropwise in 1-5 hour;
S4, dropwise after, insulation 80-90 DEG C, reaction 1-3 hour;
S5, be cooled to room temperature, use 150 mesh screen, obtain surface sizing additive.
Particularly, in step S3, monomer mixed solution comprises 1-3 kind monomer dropping component, and often kind of monomer dropping component is all formulated according to different material ratios by any one or more in hydrophobic monomer, hydrophilic monomer and cross-linking monomer.
Usefulness of the present invention is: surface sizing additive of the present invention, is a kind of polymer dispersion with inierpeneirating network structure, good stability and reactivity obtained by nanometer surfactant-free emulsion polymerization process.This surface sizing additive and size-press starch coordinate, paper and good the strengthening the property of paper products can be given, promote the ring crush intensity, burst index, folding strength etc. of paper product, can give paper good water repelling property simultaneously, solve the problem that the paper strength that causes because of weather, the moisture absorption etc. declines.
Therefore, glue sizing auxiliary agent of the present invention can meet high-strength corrugated paper, boxboard, Cultural Paper and use the paper making that intensity index has the Paper or cardboard of Improvement requirement to carry out top sizing.
Detailed description of the invention
Below in conjunction with specific embodiment, concrete introduction is done to the present invention.
Embodiment 1
Be example by 1000g, main raw material and proportioning as follows:
Monomer mixture A: styrene 180g, acrylonitrile 25g, butyl acrylate 20g, methyl methacrylate 15g, divinylbenzene 0.3g;
Monomer mixture B: acrylamide 70g, dimethylaminoethyl methacrylate 15g, acrylic acid 7g, water 50g;
Concrete preparation process is as follows:
(1), preparation one is with the four-hole boiling flask of condenser, Dropping feeder, agitator and thermometer, starch 60g, glyoxal 5g (being mixed with the aqueous solution of 40wt%) and water 450g are mixed, be warming up to 85 DEG C, be incubated 30 minutes, hierarchy of control viscosity is not higher than 10mPas.
(2) in four-hole boiling flask, add ferrous sulfate 0.12g (being dissolved in 10g water), glacial acetic acid 3g and 27wt% hydrogen peroxide 15g.Wherein, ferrous sulfate and hydrogen peroxide form initator, and glacial acetic acid is as the pH adjusting agent of system.
(3), keep temperature in 84-86 DEG C, drip monomer mixed solution A, monomer mixed solution B and hydrogen peroxide 25g (water 60g), time for adding controlled at 2 hours simultaneously.In this step, hydrogen peroxide is initator, continuous initiated polymerization.
(4), dropwise, insulation 86-88 DEG C, reacts 2 hours.
(5), be cooled to room temperature, use 150 mesh screen, obtain the faint yellow emulsion that solid content is 38.2%, viscosity is 163mPas.
Embodiment 2
Be example by 1000g, main raw material and proportioning as follows:
Monomer mixture A: styrene 140g, ethyl acrylate 25g, tert-butyl acrylate 15g, vinyl silane triisopropoxide 5g, acrylic acid 7g;
Monomer mixture B: acrylamide 60g, diallylamine 1g, water 100g;
Monomer mixture C: acryloyl-oxyethyl dimethyl benzyl ammonium chloride 10g (the 78wt% aqueous solution), water 10g.
Concrete preparation process is as follows:
(1), preparation one is with the four-hole boiling flask of condenser, Dropping feeder, agitator and thermometer, starch 90g, ɑ-amylase 0.05g, glyoxal 10g (being mixed with the aqueous solution of 40wt%) and water 450g are mixed, be warming up to 93-95 DEG C, be incubated 15 minutes, hierarchy of control viscosity is not higher than 15mPas.
(2) in four-hole boiling flask, add glacial acetic acid 3g and 27wt% hydrogen peroxide 8g.
(3), keep temperature in 75-77 DEG C, drip monomer mixed solution A, monomer mixed solution B and azo-bis-isobutyrate hydrochloride 4g (being dissolved in 80g) simultaneously, wherein the time for adding of initator controls at 3 hours, and the time for adding of monomer mixture A and B controlled at 1.5 hours.After monomer mixture A and B dropwises, then drip monomer mixture C, time for adding controls at 30min.
(4), dropwise, insulation 80-82 DEG C, reacts 2.5 hours.
(5), be cooled to room temperature, use 150 mesh screen, obtain the oyster white aqueous dispersions that solid content is 34.2%, viscosity is 120mPas.
Embodiment 3
Be example by 1000g, main raw material and proportioning as follows:
Monomer mixture A: styrene 150g, methyl methacrylate 15g, Isooctyl acrylate monomer 15g, acrylonitrile 25g, acrylic acid diethylamino ethyl ester 5, acrylic acid 7g;
Concrete preparation process is as follows:
(1), preparation one is with the four-hole boiling flask of condenser, Dropping feeder, agitator and thermometer, starch 110g, ammonium persulfate 2g, glyoxal 5g (being mixed with the aqueous solution of 40wt%) and water 550g are mixed, be warming up to 88 DEG C, be incubated 60 minutes, hierarchy of control viscosity is not higher than 20mPas.
(2), keep temperature in 90-93 DEG C, drip monomer mixed solution A and ammonium persulfate 3g (being dissolved in 100g water), wherein the time for adding of ammonium persulfate controls at 4.5 hours, and the time for adding of monomer mixture A controlled at 4 hours simultaneously.
(4), dropwise, insulation 84-86 DEG C, reacts 1 hour.
(5), be cooled to room temperature, use 150 mesh screen, obtain the oyster white aqueous dispersions that solid content is 31.2%, viscosity is 84mPas.
Performance test
Top sizing agent aid obtained for embodiment 1 to embodiment 3 is applied to paper for surface sizing, adopts 130g/m
2high-strength corrugated base paper, 110g/m
2boxboard as body paper, and contrasts with commercially available prod, and test result is respectively in table 1 and table 2, and surface sizing additive consumption is 2.5kg/ ton paper, and addition of aluminum sulfate is 5kg (liquid)/ton paper.It should be noted that, aluminum sulfate is an important source material in the coating of table glue, as a kind of effect promoter of paper sizing process, usually use together with table glue, can increase the result of use of table glue to a certain extent, this is conventional in paper table glue application, does not repeat.
Embody rule process is: a, starch gelatinization: by mass percent concentration be 8% the surface sizing starch aqueous solution heating, heat up 92 DEG C, be incubated 30 minutes, be cooled to 74 DEG C stand-by;
B, employing rod coater carry out bar type coating, and then board-like oven dry 15s, carries out measure of merit.
Wherein Cobb pH-value determination pH adopts the XSH type of Hangzhou Qingtong Boke Automation Technology Co., Ltd. can vigorous absorbability analyzer, detects pattern to be measured by GB/T1540-1989 method.
Table 1 130g/m
2the physical properties of paper of high-strength corrugated base paper
Table 2 110g/m
2the physical properties of paper of boxboard
Comparative example in table 1 and table 2 is in starch solution, add commercially available Cypres and aluminum sulfate solution, and addition and embodiment 1-3 are identical.From table 1 and table 2, surface sizing additive stability of the present invention is better, the mechanical performances such as burst index, folding strength, ring crush index are all largely increased, and the water repelling property that surface sizing additive of the present invention is good, meet the multipurpose applying glue demand of paper and paperboard, there are good market prospects.
More than show and describe general principle of the present invention, principal character and advantage.The technical staff of the industry should understand, and above-described embodiment does not limit the present invention in any form, the technical scheme that the mode that all employings are equal to replacement or equivalent transformation obtains, and all drops in protection scope of the present invention.
Claims (10)
1. a paper grade (stock) multifunction surface glue sizing auxiliary agent for enhancement mode, is characterized in that, comprises following component and the weight portion of each component is as follows:
2. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to claim 1, is characterized in that, described starch is cassava modified starch, and before use through ammonium persulfate or catalyzed by amylase degraded.
3. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to claim 1, is characterized in that, described hydrophobic monomer be styrene, α-methyl styrene, containing C
1-C
4the mixture of any one or more in substituent styrene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, tert-butyl acrylate, Isooctyl acrylate monomer, vinyl silane triisopropoxide, methyl allyl acyloxypropyl trimethoxysilane, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Tert-butyl Methacrylate and EHMA.
4. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to claim 1, it is characterized in that, described hydrophilic monomer is acrylamide, Methacrylamide, acrylonitrile, acrolein, acrylic acid, maleic anhydride, fumaric acid, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylic acid diethylamino ethyl ester, acrylate, acryloyloxyethyl trimethyl ammonium chloride, methacryloxyethyl trimethyl ammonium chloride, the mixture of any one or more in acryloyl-oxyethyl dimethyl benzyl ammonium chloride and methacryloxyethyl dimethyl benzyl ammonium chloride.
5. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to claim 1, is characterized in that, described cross-linking monomer is the mixture of any one or more in divinylbenzene, diallylamine and glycidyl methacrylate.
6. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to claim 1, it is characterized in that, described initator is the mixture of any one or more in ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, persulphate-bisulphite sodium, hydrogen peroxide, hydrogen peroxide-ferrous sulfate, hydrogen peroxide-rongalite, azo-bis-isobutyrate hydrochloride or azo diisopropylamidinateand azoles quinoline hydrochloride.
7. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to claim 1, is characterized in that, described pH adjusting agent is one or more in formic acid, glacial acetic acid, oxalic acid and aqueous sulfuric acid.
8. the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode according to any one of claim 1-7, is characterized in that, this surface sizing additive is a kind of nanoscale emulsion polymer, and solid content is 30-40%, and vitrification point is greater than 30 DEG C.
9. the preparation method of the paper grade (stock) multifunction surface glue sizing auxiliary agent of a kind of enhancement mode as described in any one of claim 1-8, is characterized in that, comprise the steps:
S1, prepare each raw material according to the parts by mass of claim 1, be mixed in reaction vessel, be warming up to 80-95 DEG C by starch, glyoxal and water, insulation 5-30 minute, hierarchy of control viscosity is not higher than 25mPas;
S2, in reaction vessel, add pH adjusting agent and part initiator;
S3, maintain the temperature at 70-95 DEG C, simultaneously or substep drip monomer mixed solution, initiator solution, dropwise in 1-5 hour;
S4, dropwise after, insulation 80-90 DEG C, reaction 1-3 hour;
S5, be cooled to room temperature, use 150 mesh screen, obtain surface sizing additive.
10. preparation method according to claim 9, it is characterized in that, in step S3, described monomer mixed solution comprises 1-3 kind monomer dropping component, and often kind of monomer dropping component is all formulated according to different material ratios by any one or more in hydrophobic monomer, hydrophilic monomer and cross-linking monomer.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732829A (en) * | 2016-02-23 | 2016-07-06 | 山东沛泽生物科技有限公司 | Starch essence |
| CN106368062A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Novel surface sizing agent and preparation method thereof |
| CN106554465A (en) * | 2016-06-29 | 2017-04-05 | 宁夏海诚电化信息科技有限公司 | A kind of top sizing agent producing process |
| CN108004841A (en) * | 2017-12-25 | 2018-05-08 | 浙江传化华洋化工有限公司 | A kind of Cypres and preparation method thereof |
| CN108329430A (en) * | 2018-01-18 | 2018-07-27 | 九洲生物技术（苏州）有限公司 | The preparation method of wrapping paper gluing reinforcing agent |
| CN108341912A (en) * | 2018-01-18 | 2018-07-31 | 九洲生物技术（苏州）有限公司 | A kind of preparation method of gluing reinforcing agent |
| CN108383944A (en) * | 2018-01-17 | 2018-08-10 | 寿光美伦纸业有限责任公司 | A kind of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions |
| CN108796815A (en) * | 2018-06-22 | 2018-11-13 | 合肥洁诺医疗用品有限公司 | A kind of non-woven fabrics for wall cloth |
| CN112553953A (en) * | 2020-12-10 | 2021-03-26 | 江门市高力依科技实业有限公司 | Surface sizing auxiliary agent and use method thereof |
-
2015
- 2015-05-29 CN CN201510289090.5A patent/CN104988796A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732829B (en) * | 2016-02-23 | 2018-02-13 | 山东沛泽生物科技有限公司 | A kind of starch extract |
| CN105732829A (en) * | 2016-02-23 | 2016-07-06 | 山东沛泽生物科技有限公司 | Starch essence |
| CN106554465A (en) * | 2016-06-29 | 2017-04-05 | 宁夏海诚电化信息科技有限公司 | A kind of top sizing agent producing process |
| CN106368062A (en) * | 2016-08-29 | 2017-02-01 | 上海东升新材料有限公司 | Novel surface sizing agent and preparation method thereof |
| CN106368062B (en) * | 2016-08-29 | 2018-03-27 | 上海东升新材料有限公司 | A kind of novel surface sizing agent and preparation method thereof |
| CN108004841A (en) * | 2017-12-25 | 2018-05-08 | 浙江传化华洋化工有限公司 | A kind of Cypres and preparation method thereof |
| CN108004841B (en) * | 2017-12-25 | 2020-10-20 | 浙江传化华洋化工有限公司 | Surface sizing agent and preparation method thereof |
| CN108383944B (en) * | 2018-01-17 | 2020-07-03 | 寿光美伦纸业有限责任公司 | Preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion |
| CN108383944A (en) * | 2018-01-17 | 2018-08-10 | 寿光美伦纸业有限责任公司 | A kind of preparation method of cationic starch/nano-cellulose base water resistant enhancing complex emulsions |
| CN108329430A (en) * | 2018-01-18 | 2018-07-27 | 九洲生物技术（苏州）有限公司 | The preparation method of wrapping paper gluing reinforcing agent |
| CN108341912B (en) * | 2018-01-18 | 2020-04-24 | 九洲生物技术（苏州）有限公司 | Preparation method of sizing reinforcing agent |
| CN108329430B (en) * | 2018-01-18 | 2020-04-24 | 九洲生物技术（苏州）有限公司 | Preparation method of sizing reinforcing agent for packaging paper |
| CN108341912A (en) * | 2018-01-18 | 2018-07-31 | 九洲生物技术（苏州）有限公司 | A kind of preparation method of gluing reinforcing agent |
| CN108796815A (en) * | 2018-06-22 | 2018-11-13 | 合肥洁诺医疗用品有限公司 | A kind of non-woven fabrics for wall cloth |
| CN112553953A (en) * | 2020-12-10 | 2021-03-26 | 江门市高力依科技实业有限公司 | Surface sizing auxiliary agent and use method thereof |
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Inventor after: Zhang Qinghui Inventor after: Fang Shijiang Inventor after: Wang Yue Inventor after: Zheng Wentao Inventor after: Zheng Chengli Inventor before: Zhang Qinghui Inventor before: Fang Shijiang Inventor before: Wang Yue |
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Effective date of registration: 20170612 Address after: 312000 Shaoxing Binhai Industrial Zone, Shaoxing, Zhejiang Applicant after: Zhejiang Hongli anti seepage glue Co., Ltd. Address before: 213022 Jiangsu city of Changzhou province Hehai new North Road No. 85 Applicant before: CHANGSHU BORUN NEW MATERIAL TECHNOLOGY CO., LTD. |
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