CN101096829B - Cation alkyl ketene dimer sizing agent and method for making same - Google Patents
Cation alkyl ketene dimer sizing agent and method for making same Download PDFInfo
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- CN101096829B CN101096829B CN2007100581353A CN200710058135A CN101096829B CN 101096829 B CN101096829 B CN 101096829B CN 2007100581353 A CN2007100581353 A CN 2007100581353A CN 200710058135 A CN200710058135 A CN 200710058135A CN 101096829 B CN101096829 B CN 101096829B
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- akd
- sizing agent
- ketene dimer
- diethylenetriamine
- alkyl ketene
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Abstract
The invention discloses a positive ion alkyl ketene dimer sizing agent and preparing method, which is characterized by the following: reacting adipic acid and diethylenetriamine; generating polyamide polyamine; reacting with AKD; generating modified AKD derivant; adopting epichlorohydrin; proceeding cationised for modified AKD derivant; getting positive ion alkyl ketene dimer sizing agent. The Zeta electric potential and charge density of the positive ion AKD emulsion are higher than non-modified AKD emulsion, which can reduce cost and increase economic benefit.
Description
Technical field
The present invention relates to a kind of sizing agent that is used for the neutral and alkali paper-making process, relate in particular to a kind of alkyl ketene dimer sizing agent, specifically, relate to a kind of kation alkyl ketene dimer sizing agent and preparation method thereof.
Background technology
Alkyl ketene dimer, English name are Alkyl Ketene Dimer, are called for short AKD, and alkyl ketene dimer sizing agent is commonly referred to the AKD sizing agent.
In paper-making process, paper is carried out the crucial operation together that the applying glue processing is a paper making wet part.Neutral and alkali applying glue technology in the neutral and alkali paper technology is a novel applying glue technology that abroad grows up the seventies in 20th century.China's paper industry is brought into use neutral and alkali applying glue technology from the eighties in 20th century, through nearly 20 years effort, the research of neutral and alkali applying glue and application have obtained and have developed rapidly, and particularly AKD neutral and alkali sizing agent is copied with the fastest developing speed in the paper technology in neutral, alkalescence.By the applying glue of AKD neutral and alkali, paper whiteness, feel, WATER RESISTANCE, physical strength, printability and resistance to ag(e)ing etc. all are significantly improved, therefore in China's paper industry, one after the other be applied in widely production of copper paperboard body paper, stamp body paper, electro-photographic paper, offset printing paper, archival paper and high culture with paper kinds such as paper in.
AKD is a kind of unsaturated lactone, and a lactonic ring and two alkyl side chains are arranged in its molecule, and fusing point is between 42~60 ℃, and is water insoluble, can be dissolved in the organic solvents such as ethanol, benzene and chloroform, and outward appearance is faint yellow waxy solid under the normal temperature.Be applied to AKD sizing agent in the slurry in the paper industry, its chemical composition is the ketene dimer of myristyl or cetyl, belongs to reactive sizing agent.Its applying glue mechanism: AKD itself has hydrophobicity long-chain fat base and reactive functional group, in AKD sizing agent sizing material adds paper pulp, because the AKD sizing agent is under the effect by cationics, keep on negatively charged fiber, the l Water Paper page or leaf is in squeezing and dry run, and the sizing material particulate evenly adsorbs and is distributed in fiber surface.The AKD fusing point is lower, in Dryer Section of Paper Machine, AKD glue fusion and under neutrality or the effect of alkaline pH value, reactive functional group base and cellulose hydroxyl generation esterification, and close with fiber frame bond, and hydrophobicity long-chain fat base turns to paper, forms hydrophobic layer, makes into paper and has high resistance water-based and sizing efficiency.
The AKD sizing agent in use, normal some problems that occur are:
(1), the AKD sizing agent is reactive sizing agent, reacts slower, needs certain curing time.
(2), because the neutral of AKD own, therefore on the paper fiber, be difficult to keep, generally need to use cationic emulsifier with AKD emulsification, AKD is adsorbed onto on the electronegative fiber with going up positive electricity.Be with the cationic agent of cationic starch as AKD in early days, but the charge density of cationic starch is lower, molecular mass is bigger, and is also lower with the bond strength of AKD particle, so the stability of emulsion and sizing efficiency are relatively poor; In addition, starch goes mouldy easily, can cause that emulsion is rotten, so sizing efficiency is often not good enough.
Some problems that in the prior art use, exist at above-mentioned AKD sizing agent, the invention provides a kind of kation alkyl ketene dimer sizing agent and preparation method thereof, use the kation alkyl ketene dimer sizing agent of the inventive method preparation, it is the cation AKD sizing agent, because of the cation AKD molecule has higher positive electricity and molecule itself has long-chain, has stronger bridge formation ability, so cation AKD is kept on fiber by Electrostatic Absorption and bridge linking effect absorption, thereby can overcome the defective that exists in the above-mentioned background technology effectively.
For realizing purpose of the present invention, the technical scheme that is adopted is: a kind of kation alkyl ketene dimer sizing agent, the polyamide polyamines and the AKD reaction that are generated by adipic acid and diethylenetriamine reaction generate modification AKD, and adopt epoxychloropropane with modification AKD cationization, and make a kind of kation alkyl ketene dimer sizing agent, be the cation AKD sizing agent, used raw material and reagent and proportioning thereof are respectively:
Chemical reagent and raw material consumption
Adipic acid, analyze pure, 5-10g
Diethylenetriamine, chemical pure, 4-10mL
Epoxychloropropane, analyze pure, 6-14mL
AKD, paper grade (stock) industrial goods, 4-10g.
Above-mentioned chemical reagent adipic acid, diethylenetriamine, the chemical structural formula of epoxychloropropane and raw material A KD is respectively:
Adipic acid
HOOC(CH
2)
4COOH
Diethylenetriamine
H
2N(CH
2)
2NH(CH
2)
2NH
2
Epoxychloropropane
Wherein, the R-alkyl is myristyl or cetyl.
The chemical structural formula of the cation AKD of making:
Wherein, the R-alkyl is myristyl or cetyl.
The method that the present invention prepares the cation AKD sizing agent is:
Chemical reagent and raw material and proportioning thereof are respectively:
Adipic acid is analyzed pure 5-10g
Diethylenetriamine, chemical pure 4-1mL
Epoxychloropropane is analyzed pure 6-14mL
AKD, paper grade (stock) industrial goods 4-10g,
Preparation method's step:
1), adipic acid and diethylenetriamine are joined in the there-necked flask that electric mixer, reflux condensing tube and thermometer are housed by consumption proportion, and there-necked flask placed constant temperature oil bath, stirring also is heated to 140 ℃~180 ℃, after isothermal reaction 2~5h and the cooling, add AKD, generate modification AKD behind reaction 2~4h
2), drip epoxychloropropane in modification AKD, react 1~3h, finish the cationization reaction of modification AKD biology, make cation AKD, its chemical structural formula:
Wherein, the R-alkyl is myristyl or cetyl.
Beneficial effect of the present invention and remarkable advantage:
AKD is a kind of waxy solid, be dissolved in some organic solvent and water insoluble, it must be emulsified into emulsion could use, therefore, above-mentioned cation AKD is added emulsifying agent and water stirs into the cation AKD white emulsion that solid content is 12-15% in dispersion machine, and be 5 with the salt acid for adjusting pH value, make it slightly to be acid, to keep stability of emulsion.
Cation AKD has higher positive electricity in the described cation AKD emulsion, and be dispersed in the emulsion, after cation AKD sizing agent of the present invention joined slurry, it is poly-that wadding at first takes place the cation AKD micelle, be adsorbed onto rapidly on the electronegative fiber surface by electrostatic adsorption then, because cation AKD has long-chain, has stronger bridge formation ability, cation AKD anchors on the fiber by bridge linking effect like this.The l Water Paper page or leaf is through behind the web part of paper machine, cation AKD is kept in the l Water Paper page or leaf, pass through drying section then, under hot conditions, the quick melting diffusion of AKD, and be evenly distributed on the fiber surface, its hydrophilic group inwardly, hydrophobic group makes page have stronger water repelling property outwardly, shows that page has obtained good sizing efficiency.
The specific embodiment
Below in conjunction with embodiment the inventive method is described in further detail.Of particular note, protection scope of the present invention should include but not limited to the disclosed technology contents of present embodiment.
Embodiment 1
6g adipic acid and 4mL diethylenetriamine are joined in the there-necked flask that electric mixer, reflux condensing tube and thermometer are housed, place the constant temperature oil bath stirring and be heated to 140~180 ℃, isothermal reaction 4h generates the polyamide polyamines, after the cooling, add 5gAKD, generate modification AKD behind the reaction 2h, drip 7mL epichlorohydrin reaction 2h again, finish the cationization reaction treatment of modification AKD.Thereby make the cation AKD that has positive electricity.
Embodiment 2
By above-mentioned same steps as, repeat embodiment 1, just the consumption with adipic acid, diethylenetriamine, AKD and epoxychloropropane is respectively 7g, 5mL, 6g and 8mL.Thereby finish the reaction treatment of the cationization of modification AKD.
Embodiment 3
By above-mentioned same steps as, repeat embodiment 1, just the consumption with adipic acid, diethylenetriamine, AKD and epoxychloropropane is respectively 8g, 6mL, 7g and 9mL.Thereby finish the reaction treatment of the cationization of modification AKD.
1, for explanation cation AKD sizing agent of the present invention has higher positive electricity, measure the Zeta potential and the charge density of sizing agent of the present invention and unmodified AKD sizing agent, measurement result compares.
The mensuration of emulsion Zeta potential: with emulsion with distilled water diluting after, on GSL-101BI type laser particle distribution recognizer, measure the Zeta potential of emulsion.
The mensuration of emulsion charge density: accurately measure emulsion after the 10ml dilution in Muteck PCD 03pH-S cylinder measuring chamber, dripping PVSK (potassium polyvinyl sulfate) standard liquid to current potential by buret is zero, is calculated the charge density of emulsion by the consumption of PVSK standard liquid.
The Zeta potential of table 1 cation AKD and unmodified AKD emulsion and charge density contrast
? | Unmodified AKD emulsion | The cation AKD emulsion |
Emulsion Zeta potential/mV | ?24.66 | ?34.36 |
Charge density/mmol/g | ?0.235 | ?0.475 |
Test result shows:
Because what Zeta potential characterized is the current potential situation of particle in the system, as shown in Table 1, find after contrast cation AKD emulsion and the unmodified AKD emulsion, it is about 30% that the Zeta potential of cation AKD emulsion is higher than unmodified AKD emulsion, and the positive electricity that the micelle in the cation AKD emulsion is described is apparently higher than unmodified AKD emulsion.In addition, the charge density of cation AKD emulsion is than exceeding of unmodified AKD emulsion nearly one times.Comprehensive above two index cation AKD sizing agents of the present invention as can be known with positive electricity obviously than the height of unmodified AKD sizing agent.
2, measure the sizing efficiency of sizing agent of the present invention and unmodified AKD sizing agent, and compare.Copy the sheet test:
Copying sheet and be by beating degree is that the sulfate bleached hardwood pulp of 35 ° of SR is copied on the standard sheet former and made, and page quantification is 80g/m
2Page after drying, slaking is 15 minutes under 105 ℃ of temperature, be cooled to room temperature after, carry out the mensuration of degree of sizing by GB/T5405-1985.
Test result shows:
When the consumption of sizing agent of the present invention was 0.2%, the page degree of sizing had reached 52s, and will reach the degree of sizing of 52s, and the consumption of unmodified AKD sizing agent then needs 0.3%, increased by 50% than sizing agent consumption of the present invention.Explanation when reaching equal sizing efficiency, the consumption of sizing agent of the present invention still less, this has reduced production cost for enterprise to a certain extent, has improved economic benefit.
Claims (3)
1. kation alkyl ketene dimer sizing agent, it is characterized in that: it is polyamide polyamines and the AKD reaction modification AKD that generates that is generated by adipic acid and diethylenetriamine reaction, and adopt epoxychloropropane with modification AKD cationization, and make a kind of kation alkyl ketene dimer sizing agent, be the cation AKD sizing agent, used raw material and chemical reagent and proportioning thereof are respectively:
Chemical reagent and raw material consumption
Adipic acid, analyze pure, 5-10g
Diethylenetriamine, chemical pure, 4-10mL
Epoxychloropropane, analyze pure, 6-14mL
AKD, paper grade (stock) industrial goods, 4-10g.
2. kation alkyl ketene dimer sizing agent according to claim 1 is characterized in that: described chemical reagent adipic acid, and diethylenetriamine, the chemical structural formula of epoxychloropropane and raw material A KD is respectively:
Adipic acid
HOOC(CH
2)
4COOH
Diethylenetriamine
H
2N(CH
2)
2NH(CH
2)
2NH
2
Epoxychloropropane
AKD
Wherein, the R-alkyl is myristyl or cetyl.
3. the preparation method of a kation alkyl ketene dimer sizing agent, used raw material and chemical reagent and proportioning thereof are in this method: adipic acid, analyze pure, 5-10g, diethylenetriamine, chemical pure, 4-10mL, epoxychloropropane, analyze pure, 6-14mL, AKD, the paper grade (stock) industrial goods, 4-10g is characterized in that: described kation alkyl ketene dimer sizing agent, and the step of its preparation method is:
1), adipic acid and diethylenetriamine are joined in the there-necked flask that electric mixer, reflux condensing tube and thermometer are housed by consumption proportion, and there-necked flask placed constant temperature oil bath, stirring also is heated to 140 ℃~180 ℃, after isothermal reaction 2~5h and the cooling, add AKD, generate modification AKD behind reaction 2~4h
2), drip epoxychloropropane in modification AKD, react 1~3h, finish the cationization reaction of modification AKD, make cation AKD, its chemical structural formula:
Wherein, the R-alkyl is myristyl or cetyl.
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Families Citing this family (4)
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CN102020771B (en) * | 2009-09-18 | 2013-05-22 | 中国石油化工股份有限公司 | Grafted polyether high-molecular polymer, and preparation method and application thereof |
CN105113327A (en) * | 2015-08-13 | 2015-12-02 | 合肥龙发包装有限公司 | Preparation method for AKD gel emulsifier |
CN105908567B (en) * | 2016-04-26 | 2017-09-19 | 齐鲁工业大学 | A kind of preparation method of surfactant-free alkyl ketene dimer emulsion |
CN108691245B (en) * | 2018-05-25 | 2020-07-07 | 浙江恒川新材料有限公司 | Preparation method of high-electronegativity AKD (alkyl ketene dimer) internal sizing agent |
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US3223544A (en) * | 1963-03-19 | 1965-12-14 | American Cyanamid Co | Manufacture of cationic paper sizing ketene dimer emulsions |
CN1314202A (en) * | 2000-03-16 | 2001-09-26 | 中国科学院成都有机化学研究所 | Self emulsion AKD and its preparing method |
CN1346417A (en) * | 1999-04-15 | 2002-04-24 | 阿克佐诺贝尔公司 | Sizing composition |
CN1727377A (en) * | 2005-07-28 | 2006-02-01 | 陕西科技大学 | Method for preparing compound emulsion of dimmer of cation polyurethane and alkyl ketene |
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2007
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US3223544A (en) * | 1963-03-19 | 1965-12-14 | American Cyanamid Co | Manufacture of cationic paper sizing ketene dimer emulsions |
CN1346417A (en) * | 1999-04-15 | 2002-04-24 | 阿克佐诺贝尔公司 | Sizing composition |
CN1314202A (en) * | 2000-03-16 | 2001-09-26 | 中国科学院成都有机化学研究所 | Self emulsion AKD and its preparing method |
CN1727377A (en) * | 2005-07-28 | 2006-02-01 | 陕西科技大学 | Method for preparing compound emulsion of dimmer of cation polyurethane and alkyl ketene |
Non-Patent Citations (5)
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JP昭60-88196A 1985.05.17 |
戴红旗 等.烷基烯酮二聚体化学改性及其应用探讨.造纸化学品 3.2002,(3),31-33. |
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