CN104120626B - A kind of sizing agent and its preparation method and application - Google Patents
A kind of sizing agent and its preparation method and application Download PDFInfo
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- CN104120626B CN104120626B CN201410328290.2A CN201410328290A CN104120626B CN 104120626 B CN104120626 B CN 104120626B CN 201410328290 A CN201410328290 A CN 201410328290A CN 104120626 B CN104120626 B CN 104120626B
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Abstract
The present invention relates to a kind of novel sizing agent and its preparation method and application, sizing agent prepares as follows: (1) makes hexadecylic acid and diethylenetriamine in the presence of a catalyst and react at temperature 90 ~ 180 DEG C to obtain fatty acid amide in 3 ~ 10 hours, and wherein hexadecylic acid is 0.1 ~ 20:1 with the mass ratio that feeds intake of diethylenetriamine；(2) step (1) gained fatty acid amide is joined in reaction vessel, control temperature between 50 DEG C ~ 95 DEG C and under stirring, add dimethyl carbonate and sodium hydroxide, fatty acid amide is 0.05 ~ 25:1 with the mass ratio that feeds intake of dimethyl carbonate, fatty acid amide is after 0.1 ~ 30:1 adds with the mass ratio of sodium hydroxide, continue reaction 2 ~ 7 hours, obtain sizing agent.Sizing agent of the present invention can be used not only for starching interior interpolation, it is also possible to for top sizing, which kind of occupation mode can be greatly improved the water-resistance of paper regardless of, can increase the surface strength of paper simultaneously.Taking the Paper or cardboard water-resistance after glue applying method applying glue of the present invention good, surface strength is high.
Description
Technical field
The present invention relates to a kind of sizing agent and its preparation method and application.
Background technology
At present, along with fast development and the improving constantly of people's living standard of science and technology, people to various not
The performance requirement of the paper of congenerous is more and more higher.In order to meet the application demand of people, paper plant is necessary for by various sides
Formula improves the product quality of oneself, such as in order to improve water-resistance and the surface strength of paper, often uses the mode of applying glue
So that paper performance reaches requirement.The resin application methods of present commonplace use is broadly divided into two kinds: plasm-glue-blending and surface are executed
Glue.
The mode added in slurry is the wet end interpolation sizing agent at paper machine, and kind is mainly neutral-to-alkaline sizing agents such as alkyl alkene
Ketone dimer (is called for short AKD), alkenyl succinic anhydride (being called for short ASA) etc..But the sizing agent added in slurry is easily by working condition
Such as the impact of the factor such as shearing when water quality, pH value, temperature and pumping, so the retention of sizing agent and application effect all can
By a certain degree of impact.Additionally, AKD and ASA molecule is nonionic Organic substance, all without electropositivity, need first to borrow
Helping cationic emulsifier and fiber could be formed adsorption, then AKD and ASA reacts with cellulosic hydroxy thus is bonded to
Fiber surface；AKD and ASA another problem in use is susceptible to hydrolysis exactly, and this allows for them can not be good
Apply in paper production.
The occupation mode of another sizing agent is top sizing.Top sizing is exactly to apply a certain amount of on the surface becoming paper
Sizing agent, with slurry in add sizing agent compared with, Cypres has many good qualities: it is not by copy paper water quality and the shadow of water temperature
Ring, stable degree of sizing can be obtained；Reduce the consumption of sizing agent, reduce production cost, and reduce the obstacles such as machinery contamination, can
So that paper machine system more cleans, reduce the COD of paper machine white water；The effect of Cypres plays and need not ripening etc..At present,
Using more Cypres can be divided into natural polymer subclass, such as modified starch, and the surface of synthesized polymer species is executed
Colloid, such as water-soluble polymer Cypres, (styrene maleic anhydride copolymer is called for short SMA and styrene acrylic copolymerization
Thing, is called for short SAA).But these Cypres also have respective shortcoming, modified starch is the most hydrophilic owing to containing on strand
The hydroxyl of property, although so the paper surface strength processed with such sizing agent increases but water-resistance is the most poor.
SMA, SAA are anionic polymer, it is impossible to use in low ph conditions, and often will be by some cationic substance ability
Play a role.It addition, this series products in use can produce a large amount of foam, thus affect stablizing of size press effect
Property, limit its application in paper industry.
Summary of the invention
The technical problem to be solved overcome the deficiencies in the prior art, it is provided that a kind of new sizing agent, this is executed
Colloid can be used not only for starching interior interpolation, it is also possible to for top sizing, and no matter which kind of occupation mode can be greatly improved
The water-resistance of paper, can increase the surface strength of paper simultaneously.
The present invention also provides for the preparation method and application of this sizing agent simultaneously.
For solving problem above, a kind of technical scheme that the present invention takes is as follows:
A kind of sizing agent shown in formula (I),
The another technical scheme that the present invention takes is: the preparation method of a kind of sizing agent, it comprises the steps:
(1) make hexadecylic acid and diethylenetriamine in the presence of a catalyst and react 3～10 hours at temperature 90～180 DEG C
Obtain the fatty acid amide shown in formula (II),
CH3(CH2)14CONHCH2CH2NHCH2CH2NHOC(CH2)14CH3(II),
Wherein hexadecylic acid is 0.1～20:1 with the mass ratio that feeds intake of diethylenetriamine；
(2) step (1) gained fatty acid amide is joined in reaction vessel, control temperature between 50 DEG C～95 DEG C and
Under stirring, adding dimethyl carbonate and sodium hydroxide, fatty acid amide is 0.05～25:1 with the mass ratio that feeds intake of dimethyl carbonate,
The mass ratio of fatty acid amide and sodium hydroxide is 0.1～30:1, after addition, continues reaction 2～7 hours, obtain described in execute
Colloid.
Reaction equation involved by step (2) is expressed as follows
In step (1), catalyst adds with the amount of catalysis, and usually hexadecylic acid and diethylenetriamine feed intake quality sum
0.01%～10%, preferably 0.1%～2%.Catalyst can be selected from sodium fluoride, Feldalat NM, Sodium ethylate, p-methyl benzenesulfonic acid
In the combination of one or more, quality sum that the addition quality of catalyst is described fatty acid and diethylenetriamine feeds intake
0.1%～2%.Preferably catalyst is p-methyl benzenesulfonic acid.
In step (1), preferred reaction temperature is 130～155 DEG C.The preferably response time is 4～8 hours.
In step (2), preferred reaction temperature is 65 DEG C～85 DEG C, and the preferred response time is 2～5 hours.
Preferably, fatty acid amide is 1～10:1 with the mass ratio that feeds intake of dimethyl carbonate, and more preferably 2～8:1 enter one
Step is preferably 3～6:1.Preferably, fatty acid amide is 1～20:1 with the mass ratio that feeds intake of sodium hydroxide, it is highly preferred that fatty acyl
Amine is 10～20:1 with the mass ratio that feeds intake of sodium hydroxide.
The present invention also provides for a kind of glue application solution, and it is mixed by sizing agent, emulsifying agent and the water that the present invention is above-mentioned, its
In, described emulsifying agent and water account for 0.1wt%～40wt% and 1wt%～95wt% of described glue application solution respectively.
Further, emulsifying agent can be cation, and anion or non-ionic macromolecular compound mainly has height
Level fatty acid, high fatty alcohol and their ester；The fatty alcohol-polyoxyethylene ether of nonionic, alkylphenol polyoxyethylene etc.；
The alkyl sodium sulfate of anionic, sodium alkyl sulfonate and quaternary ammonium cation type.Concrete such as cationic starch, polyamine, polyamides
Amine epoxychloropropane etc..
The application of sizing agents of present invention Surface sizing mechanism on paper is as follows: owing to this sizing agent is cationic quaternary ammonium
The compound of salt, itself belonging to is from curable type sizing agent, so when this material is applied on paper, electronegative fiber
First fatty acid amide sizing agent generation Electrostatic Absorption with band positive charge sizing agent can be made to anchor at the surface of fiber, and this applying glue
The long carbon alkyl chain of agent can spread over the surface of paper and then play hydrophobic, the effect of water resistant.
Further, the sizing agent that the present invention relates to can be used alone in actual application, it is also possible to other
Sizing agent is compounding together to be used, can be with plasm-glue-blending, it is also possible to top sizing.To this end, the invention still further relates to a kind of paper and/or paper
Plate glue applying method, takes plasm-glue-blending mode or top sizing mode, and the sizing agent that the method uses is including at least in the present invention
The sizing agent stated.Moreover, it relates to by the paper after the method applying glue and/or cardboard.
Further, described Paper or cardboard can be cultural paper, industrial paper, package paper, information paper using and spy
Different paper using, such as: art paper, LWC, printing paper；Kraft liner, corrugating medium, coated white paperboard, chipboard；Wrapping paper, bag
Use kraft paper；Autotype paper, facsimile transmission paper, no carbon paper；Bank-note paper etc..And this Paper or cardboard is quantification of more than 15g/m2。
It addition, the body paper of Paper or cardboard involved in the present invention is when manufacturing paper with pulp, the raw material used can be pure wood pulp, straw pulp, bamboo pulp,
Bagasse, agricultural crop straw, reclaims slurry, the mixture of any one or a few slurry therein such as mineral filler.
According to a specific aspect, the surface sizing method of described Paper or cardboard is as follows: by body paper by sizing applicator requirement
Smooth is placed on sizing applicator, depresses idler roller, then application roll is pressed in top of form, put down fixed-wing, by applying glue of the present invention
Emulsion (glue application solution as above-mentioned in the present invention) that agent is made into and the good Oxytarch of gelatinizing or enzyme converted starch compounding after so that it is all
Even is distributed in top of form, start button, completes the applying glue of paper.
According to a specific aspect, the plasm-glue-blending method of described Paper or cardboard is as follows: according to the required paper manufactured paper with pulp
The quantitative requirement opened, weighs a certain amount of certain density slurry prepared, and the emulsion being made into by sizing agent of the present invention is (such as this
Invent above-mentioned glue application solution) join in slurry, stir, handsheet.Certainly according to demand can also be during handsheet
Add other chemicals, such as drying strengthening agent, wet strength agent, retention agent etc..
Due to the employing of above technical scheme, the present invention compared with prior art has the advantage that
Sizing agent of the present invention can be used not only for starching interior interpolation, it is also possible to for top sizing, regardless of which kind of occupation mode
The water-resistance of paper can be greatly improved, the surface strength of paper can be increased simultaneously.
Prepared gained sizing agent by the preparation method of sizing agent of the present invention to overcome existing sizing agent and can only take one
The deficiency of resin application methods, can be greatly improved the water-resistance of paper regardless of which kind of occupation mode, can increase paper simultaneously
Surface strength, and this application of sizing agents scope is wide.
Taking the Paper or cardboard water-resistance after glue applying method applying glue of the present invention good, surface strength is high.
Detailed description of the invention
The sizing agent of the present invention is compared with existing synthesis class sizing agent (AKD, ASA), although three is can be with fibre
The reactive sizing agent of dimension reaction, but exist the most dramatically different:
1, AKD is nonionic Organic substance, needs fiber to be formed adsorption by cationic emulsifier, secondly,
The reactivity of AKD is more weak, and reacting with fiber surface hydroxyl generates β-carbonyl ester, and this reaction needs the regular hour
And temperature, so AKD applying glue is used to there will be applying glue hysteresis.
2, ASA is nonionic Organic substance, it is also desirable to fiber could be formed adsorption by cationic emulsifier, its
Secondary, ASA reactivity is strong, and poor stability, easily with the substance reaction containing active hydrogen, can quickly produce hydrolysis as contacted with water,
So using ASA to need on-the-spot emulsifying.
3, the sizing agent that the present invention relates to belongs to the compound of cationic quaternary ammonium salt, compared with AKD and ASA, it is not necessary to borrow
The material helping other just can adsorb on fiber, is a kind of without applying glue hysteresis, and the glue used in paper-making of stable performance.
4, there is the phenomenon of hydrolysis in sizing agent of the present invention, ASA and AKD, but sizing agent hydrolysis rate of the present invention is slower than AKD
And ASA, hydrolyzate has cationic, remains to adsorb on fiber, so the impact on using is the least, and AKD and ASA
Hydrolysis amplitude wants big many, can significantly affect use.
5, sizing agent of the present invention both may be used for starching interior interpolation and can be used for top sizing, and AKD is for top sizing
Not only there is the maturation period, and owing to its essence is wax, the coefficient of friction of paper surface can be reduced, thus affect paper at printer
On runnability.
Below in conjunction with specific embodiment, the present invention is described in further details.Should be understood that these embodiments are for saying
The ultimate principle of the bright present invention, principal character and advantage, and the present invention is not limited by the following examples.Embodiment uses
Implementation condition can do adjustment further according to specific requirement, and not marked implementation condition is usually the condition in normal experiment.
Embodiment 1
1, the preparation of sizing agent
The first step: the synthesis of fatty acid amide
A certain amount of reactant hexadecylic acid is added in equipped with the 1000ml four-hole boiling flask of agitator, thermometer and condensing tube
With diethylenetriamine, and a small amount of p-methyl benzenesulfonic acid, wherein hexadecylic acid is 4:1 with the mass ratio of diethylenetriamine, to toluene
The addition of sulfonic acid is the 0.8% of the quality summation of above-mentioned reactant, and by three's mix homogeneously, heating makes the temperature of system be
150 DEG C, the response time is 6 hours, makes reaction complete, and the product of final gained is fatty acid amide.
Second step: fatty acid amide cation-modified
Equipped with in the 1000ml four-hole boiling flask of agitator, thermometer, Dropping funnel and condensing tube, add the first step and prepare
Fatty acid amide, adjust temperature, the temperature making system is 75 DEG C, from Dropping funnel drip a certain amount of dimethyl carbonate, make fat
Fat amide is 3:1 with the mass ratio of dimethyl carbonate, adds a certain amount of sodium hydroxide simultaneously, make fatty acyl in reaction system
Amine and the mass ratio 15:1 of sodium hydroxide, continue reaction 3 hours, complete cation-modified, obtain sizing agent after dripping.
2, the preparation of glue application solution
Weigh above-mentioned cation fatty acid amide, emulsifying agent polyamideepichlorohydrin and water, by three according to mass ratio 9:
The ratio mix homogeneously of 9:82.
3, the preparation of the handsheet containing this sizing agent
The hardwood pulp that freedom is 450ml and softwood pulp that freedom is 550ml according to absolute dry mass than for 8:2
Mix, be made into the pulp solution that concentration is 1.2%, weigh a certain amount of above-mentioned glue application solution and join in slurry and stir
Uniformly, weigh this slurry handsheet a certain amount of and make the quantification of 80g/m of handsheet2, over dry glue application solution and the quality of oven dry stock
Ratio is 0.2%.
In order to highlight the distinctive technique effect of sizing agent prepared by the present invention, the present invention is by homemade sizing agent and city
Carry out application experiment together with AKD with the ASA sizing agent sold, weigh three kinds of sizing agents of identical oven-dry weight the most respectively, mix with slurry
Closing, handsheet, then compare the application effect of three, sizing stability and applying glue hysteresis quality, concrete experimental result is as follows:
1) mill size and the application effectiveness comparison of AKD and ASA, see table 1.
The application effectiveness comparison of 1 three kinds of sizing agents of table
2) mill size compares with the stability of AKD and ASA, sees table 2.
The 2 three kinds of sizing agents of table stability under 60 DEG C of conditions of storage compares
3) mill size compares with the applying glue hysteresis quality of AKD, sees table 3.
The applying glue hysteresis quality of 3 two kinds of sizing agents of table compares
Embodiment 2
1, the preparation of sizing agent
The first step: the synthesis of fatty acid amide
A certain amount of reactant hexadecylic acid is added in equipped with the 1000ml four-hole boiling flask of agitator, thermometer and condensing tube
With diethylenetriamine, and a small amount of sodium fluoride, wherein hexadecylic acid is 5:1 with the mass ratio of diethylenetriamine, adding of sodium fluoride
Dosage is the 1.2% of the quality summation of above-mentioned reactant, and by three's mix homogeneously, heating makes the temperature of system be 160 DEG C, reaction
Time is 5 hours, makes reaction complete, and the product of final gained is fatty acid amide.
Second step: fatty acid amide cation-modified
Equipped with in the 1000ml four-hole boiling flask of agitator, thermometer, Dropping funnel and condensing tube, add the first step and prepare
Fatty acid amide, adjust temperature, the temperature making system is 70 DEG C, from Dropping funnel drip a certain amount of dimethyl carbonate, make fat
Fat amide is 4:1 with the mass ratio of dimethyl carbonate, adds a certain amount of sodium hydroxide simultaneously, make fatty acyl in reaction system
Amine and the mass ratio 12:1 of sodium hydroxide, continue reaction 3 hours, complete cation-modified, obtain sizing agent after dripping.
2, the configuration of surface size
The present embodiment uses the good Oxytarch of gelatinizing and homemade sizing agent to be combined together use, Oxytarch with from
The absolute dry mass of control surface sizing agent is than for 97:3, and the concentration of surface size is 8%, and the temperature of surface size is 60 DEG C.
Wherein, mill size is really executed according to the ratio of mass ratio 11:8:81 is mixed with fatty alcohol-polyoxyethylene ether and water
Colloid.
Note: the gelatinizing technique of Oxytarch is as follows: add suitable quantity of water in reaction flask, Oxytarch is slowly added to,
Uniform stirring, is heated to 90 DEG C, is incubated 15min, and being cooled to 60～70 DEG C can use.
3, the preparation of the paper containing this sizing agent
By quantification of 50g/m2Body paper by smooth being placed on sizing applicator of sizing applicator requirement, depress idler roller, then executing
Rubber roll is pressed in top of form, puts down fixed-wing, and a certain amount of glue application solution is evenly distributed in top of form, controls resin added and is
1.5g/m2, start button, complete the applying glue experiment of paper.The paper completing applying glue is placed on laboratory with constant temperature and constant humidity equilibrium water
The detection of paper physical property is carried out after dividing 24 hours.
In order to highlight the distinctive technique effect of sizing agent prepared by the present invention, the present invention is by homemade sizing agent and city
The SMA sizing agent sold carries out application experiment together, and i.e. both are combined together than with Oxytarch with identical absolute dry mass and make
With, then comparing both application effects, concrete experimental result sees table 4:
The application effectiveness comparison of 4 two kinds of sizing agents of table
Above-described embodiment, only for technology design and the feature of the explanation present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implements according to this, can not limit the scope of the invention with this, all according to the present invention
The equivalence that spirit is made changes or modifies, and all should contain within protection scope of the present invention.
Claims (3)
1. a glue application solution, it is characterised in that: it is mixed by sizing agent, emulsifying agent and water, described emulsifying agent and moisture
Do not account for 0.1wt% ~ 40 wt % and the 1wt % ~ 95wt % of described glue application solution；Described emulsifying agent is selected from: higher fatty acids, senior
Fatty alcohol and their ester；The fatty alcohol-polyoxyethylene ether of nonionic, alkylphenol polyoxyethylene；The alkyl sulfide of anionic
Acid sodium, sodium alkyl sulfonate and quaternary ammonium cation type emulsifying agent；
The structural formula of described sizing agent is as shown in the formula (I)
；
The preparation method of described sizing agent comprises the steps:
(1) make hexadecylic acid and diethylenetriamine in the presence of a catalyst and react at temperature 90 ~ 180 DEG C to obtain formula in 3 ~ 10 hours
(II) fatty acid amide shown in,
CH3(CH2)14CONHCH2CH2NHCH2CH2NHOC(CH2)14CH3(II),
Wherein hexadecylic acid is 0.1 ~ 20:1 with the mass ratio that feeds intake of diethylenetriamine；
(2) step (1) gained fatty acid amide is joined in reaction vessel, control temperature and and stir between 65 DEG C ~ 85 DEG C
Under, adding dimethyl carbonate and sodium hydroxide, fatty acid amide is 0.05 ~ 25:1 with the mass ratio that feeds intake of dimethyl carbonate, fat
Amide is 0.1 ~ 30:1 with the mass ratio of sodium hydroxide, after addition, continues reaction 2 ~ 5 hours, obtains described sizing agent；
In step (1), described catalyst is selected from sodium fluoride, Feldalat NM, the combination of one or more in Sodium ethylate, described in urge
The addition quality of agent is that described fatty acid and diethylenetriamine feed intake the 0.1% ~ 2% of quality sum.
Glue application solution the most according to claim 1, it is characterised in that: in step (1), make reaction at temperature 130 ~ 155 DEG C
Carrying out, the response time is 4 ~ 8 hours.
3. the application in paper and/or cardboard applying glue of the glue application solution described in claim 1.
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| CN108221474A (en) * | 2018-01-11 | 2018-06-29 | 石家庄德旺科技有限公司 | A kind of preparation method of new paper making glue |
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| CN101435173B (en) * | 2008-12-22 | 2010-11-10 | 陕西科技大学 | Paper making neutral sizing agent and preparing method thereof |
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